TW202216799A - Shelf life stable and improved mass polymerizable polycyclic-olefinic compositions - Google Patents

Abstract

Embodiments in accordance with the present invention encompass compositions containing one or more polycycloolefinic monomers, optionally at least one multifunctional olefinic monomer and a suitable solvent, which exhibits long shelf life stability and undergoes mass polymerization only when subjected to a suitable temperature to provide a three-dimensional insulating articles. Embodiments of this invention exhibit hitherto unattainable properties, such as for example, low dielectric constant and low loss properties, and very high thermal properties, among others. The compositions of this invention may additionally contain one or more organic or inorganic filler materials, which provide improved thermo-mechanical properties in addition to very low dielectric properties. In general the compositions are stable at room temperature for an extended period of time lasting up to a few weeks and undergo mass polymerization only when subjected to suitable higher temperatures generally above 100 ºC. The compositions of this invention are useful in various applications, including as insulating materials in millimeter wave radar antennas, among others.

Description

Shelf life stable and bulk polymerizable improved polycycloolefin compositions

Embodiments according to the present invention generally relate to a composition comprising more than one polycycloolefin monomer, an organic palladium catalyst, an activator and a solvent. The composition may include more than one multifunctional olefin monomer. The composition is very stable under ambient conditions and thus exhibits long shelf life stability. However, the composition undergoes instant bulk polymerization at suitable high temperatures to form three-dimensional insulating products exhibiting hitherto unachievable low dielectric constant, low loss properties, and very high thermal properties. More specifically, the present invention relates to a composition comprising a series of substituted norbornene derivatives, a solvent and, as required, one or more bifunctional monomeric compounds, which composition is carried out in the presence of a specific organopalladium compound. Bulk polymerization to form three-dimensional products, such as films, which exhibit extremely high glass transition temperatures, which can be as high as 300°C or more, and exhibit low dielectric constant (less than 2.4 at a frequency of 10 GHz) and low loss characteristics. Accordingly, the compositions of the present invention can be used as insulating materials in a variety of applications, including electromechanical devices used in the manufacture of various automotive parts. [Cross-reference to related applications]

This application claims the benefit of US Provisional Application No. 63/107,522, filed October 30, 2020, the entire contents of which are incorporated herein by reference.

It is well known in the art that insulating materials with low dielectric constant (Dk) and low loss (Df) are important in printed circuit boards for electrical appliances, automotive parts and other applications. Typically, in most such devices, a suitable insulating material must have a dielectric constant of less than 3 and a low loss of less than 0.002 (or less than 0.001) at high frequencies (eg, above 50 GHz). In addition, since organic dielectric materials have advantages such as being easy to manufacture, interest in developing organic dielectric materials has been increasing day by day.

However, there are significant challenges in developing such insulating materials that meet all requirements. One of the challenges is that such materials show low coefficients of thermal expansion (CTE) in the range of 50 to 100 ppm/K, due to delamination from the copper layer. Another challenge is that these materials exhibit a very high glass transition temperature (T _g ), given the processing conditions utilized in the manufacture of printed circuit boards and the harsh conditions the device may encounter (such as the use of mmWave radars in automobiles). antenna), so the glass transition temperature is preferably higher than 150°C or higher than 250°C.

For example, films formed by addition polymerization of norbornene derivatives containing long side chains such as 5-hexylnorbornene (HexNB) and 5-decylnorbornene (DecNB), although have low hydrophobicity Dk and Df, but these films show high CTE (>200 ppm/K) and low _Tg . For example, refer to JP2016037577A and JP2012121956A.

For example, polymers with low Dk/Df such as fluorinated polyethylene, polyethylene and polystyrene are also described in the literature, but these polymers exhibit extremely low glass transition temperatures (which can be well below 150°C) , so it is not suitable as an organic insulating material. In addition, it is also described in the literature that when combined with substituted norbornenes substituted with polar groups such as ester groups or alcohol groups, polymers with low CTE and high T _g are generally produced. However, due to the polarizability of such groups in electromagnetic fields, especially at high frequencies, the incorporation of such groups results in high Dk and Df. Therefore, norbornenes substituted with such polar groups are not suitable for forming the insulating materials contemplated in this specification.

Therefore, there is still a need to develop a new insulating material that exhibits not only low dielectric properties but also high thermal properties.

Therefore, an object of the present invention is to provide a composition containing one or more substituted norbornene monomers and a multifunctional monomer, which provides an insulating material having characteristics that have not been achieved so far when subjected to bulk polymerization.

Hereinafter, other objects and further scope of application of the present invention will be described in detail. [Inventive effect]

Surprisingly, it has now been found that by using a composition comprising more than one monomer of the general formula (I) above, a solvent, an organopalladium compound and an activator (i.e. a cocatalyst), it is possible to form a composition that can be obtained so far. Three-dimensional products with unrealized dielectric properties, thermal properties, and other enhanced properties. In some embodiments, as described in this specification, the composition may further comprise at least one polyfunctional compound of general formula (A1) or (A2) or (A3). Therefore, the compositions of the present invention can be used to manufacture various electronic devices, optical devices and optoelectronic devices. More specifically, the compositions of the present invention can be used as coating materials, filler materials and for forming various three-dimensional products, such as films and other solid products.

In another aspect of the present invention, there is also provided a kit comprising the composition of the present invention.

Terms used in this manual have the following meanings:

Unless otherwise specified to be limited to one referent, the articles "a (a/an)" and "the (the)" used in this specification include plural referents.

Since all numbers, numerical values and/or expressions relating to the amounts of ingredients, reaction conditions, etc. used in this specification and the scope of the claims appended hereto will encounter various measurement uncertainties in obtaining the aforementioned values, unless otherwise specified, Otherwise, it should be understood as modified by the term "about" in all cases.

Numerical ranges disclosed in this specification are continuous and include the minimum and maximum values of the range, and every value between the foregoing minimum and maximum values. In addition, when a range is an integer, every integer between the minimum value and the maximum value of the said range is included. Additionally, when multiple ranges are provided to describe a characteristic or characteristic, the ranges may be combined. In other words, all ranges disclosed in this specification should be understood to include any range and all sub-ranges it has, unless otherwise stated. For example, a specified range from "1 to 10" should be considered to include any range and all subranges between a minimum value of 1 and a maximum value of 10. Exemplary subranges of the range 1-10 include, but are not limited to, 1-6.1, 3.5-7.8, 5.5-10, and the like.

As used in this specification, "hydrocarbyl" refers to a group containing carbon atoms and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbyl group having at least one hydrogen replaced by a halogen. The term "perhalocarbyl" refers to a hydrocarbyl group in which all hydrogens have been replaced by halogens.

The expression "alkyl" as used in this specification refers to a saturated, straight or branched chain hydrocarbon substituent having the specified number of carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, tertiary butyl and the like. Derivative expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl" ", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl" and "phenoxyalkyl" should also be construed accordingly.

The expression "cycloalkyl" as used in this specification includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derivative expressions such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl" and "cycloalkylcarbonyl" are also to be interpreted accordingly.

The expression "perhaloalkyl" as used in this specification refers to the above-mentioned alkyl group in which all hydrogen atoms in the alkyl group are replaced by halogen atoms selected from fluorine, chlorine, bromine or iodine. Illustrative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and linear or branched Fluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl and the like. The derived expression "perhaloalkoxy" is also to be interpreted accordingly. It should be further noted that some of the alkyl groups described in this specification may be partially fluorinated, that is, only the hydrogen atoms in the aforementioned alkyl groups are partially replaced by fluorine atoms, and should be construed accordingly

The expression "alkanoyl group" used in this specification shall have the same meaning as "alkanoyl group", which can also be represented as "R-CO-" in structure, wherein R is described in this specification and has a specified number of carbon atoms the "alkyl". In addition, the meaning of "alkylcarbonyl" should be the same as that of "acyl group" described in this specification. Specifically, the "(C ₁ -C ₄ ) acyl group" refers to a methanoyl group, an acetyl group (acetyl/ethanoyl), a propionyl group, a n-butyl group, and the like. Derivative expressions such as "alkoxy" and "alkoxyalkyl" are also to be construed accordingly.

The expression "aryl" as used in this specification refers to a substituted or unsubstituted phenyl or naphthyl group. Specific examples of the substituted phenyl group or the substituted naphthyl group include o-tolyl, p-tolyl, m-tolyl, 1,2-xylyl, 1,3-xylyl, 1,4-xylyl , 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" also includes any available substituents as further defined in this specification or known in the art.

The expression "arylalkyl" used in this specification means that the above-mentioned aryl group is further attached to the above-mentioned alkyl group. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

The expression "alkenyl" used in this specification refers to an acyclic, straight or branched hydrocarbon chain having a specified number of carbon atoms and at least one carbon-carbon double bond, including vinyl and straight or branched propylene group, butenyl, pentenyl and hexenyl. The derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" are also to be interpreted accordingly. Illustrative examples of such derivative expressions include furan-2-vinyl, phenylvinyl, 4-methoxyphenylvinyl, and the like.

The expression "heteroaryl" as used in this specification includes all known heteroatom-containing aromatic groups. Representative 5-membered heteroaryl groups include furyl, thienyl or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like. Representative 6-membered heteroaryl groups include pyridyl, pyridyl, pyrimidinyl, pyridyl, tris'yl, and the like. Representative examples of bicyclic heteroaryl groups include benzofuranyl, benzphenylthio, indolyl, quinolinyl, isoquinolinyl, cinnolinyl, benzimidazolyl, indazolyl, pyridylfuryl, Pyridinethienyl, etc.

啉基、硫代

啉基等。各種其他雜環基包括氮丙啶基（aziridinyl）、氮雜環庚烷基（azepanyl）、二氮雜環庚烷基（diazepanyl）、二氮雜雙環[2.2.1]庚-2-基、三氮雜環辛烷基（triazocanyl）等，但並不限於此。As used in this specification, the expression "heterocycle" includes all known cyclic groups containing reduced heteroatoms. Representative 5-membered heterocyclyl groups include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative 6-membered heterocyclyl groups include piperidinyl, piperidine,

Lino, thio

Lino, etc. Various other heterocyclyl groups include aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]heptan-2-yl, Triazocanyl, etc., but not limited thereto.

"Halogen" or "halo" refers to chlorine, fluorine, bromine and iodine.

Broadly, the term "substituted" is considered to include all permissible substituents of organic compounds. In some embodiments disclosed in this specification, the term "substituted" refers to substitution with one or more substituents independently selected from the group consisting of (C ₁ -C ₆ ) alkyl, (C ₂ -C ) ₆ ) Alkenyl, (C ₁ -C ₆ ) perfluoroalkyl, phenyl, hydroxyl, -CO ₂ H, ester, amide, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) The group of thioalkyl and (C ₁ -C ₆ )perfluoroalkoxy. However, any other suitable substituents known to those skilled in the art can also be suitable for use in these embodiments.

It should be noted that any atom having an unsatisfactory valence in the text, schemes, examples and tables of this specification is assumed to have an appropriate number of hydrogen atoms to satisfy the aforementioned valence.

In this specification, the terms "dielectric" and "insulating" should be understood to be used interchangeably. Thus, references to insulating materials or insulating layers include dielectric materials or layers, and vice versa. Additionally, the term "organic electronic device" as used in this specification should be understood to include the term "organic semiconductor device" and multiple instances of such devices as used, for example, in the automotive industry.

The dielectric constant (Dk) of a material used in this specification is the ratio of the charge stored in the insulating material between two metal plates to the charge that can be stored when the insulating material is replaced by vacuum or air. It is also called permittivity. It is sometimes called relative permittivity because relative measurements are made based on the permittivity of free space.

As used in this specification, "low loss" refers to the dissipation factor (Df) which determines the rate of energy loss in an oscillating mode (mechanical, electrical or electromechanical) in a dissipative system. It is the inverse of the figure of merit and stands for "quality" or oscillation persistence.

The term "derived" means that a polymerizable repeating unit is polymerized (formed) from a polycyclic norbornene-type monomer, for example, according to the general formula (I), wherein the obtained polymer is obtained by means of the norbornene-type monomer shown below. A 2,3-matched connection of the body is formed:

（I） 其中， m為0、1或2的整數；

為單鍵或雙鍵； R ₁、R ₂、R ₃及R ₄相同或不同，並且各自獨立地選自包括氫、鹵素、甲基、乙基、直鏈或支鏈（C ₃-C ₁₆）烷基、全氟（C ₁-C ₁₂）烷基、（C ₃-C ₁₂）環烷基、（C ₆-C ₁₂）雙環烷基、（C ₇-C ₁₄）三環烷基、（C ₆-C ₁₀）芳基、（C ₆-C ₁₀）芳基（C ₁-C ₆）烷基、全氟（C ₆-C ₁₀）芳基、全氟（C ₆-C ₁₀）芳基（C ₁-C ₆）烷基、甲氧基、乙氧基、直鏈或支鏈（C ₃-C ₁₆）烷氧基、環氧（C ₁-C ₁₀）烷基、環氧（C ₁-C ₁₀）烷氧基（C ₁-C ₁₀）烷基、環氧（C ₃-C ₁₀）環烷基、全氟（C ₁-C ₁₂）烷氧基、（C ₃-C ₁₂）環烷氧基、（C ₆-C ₁₂）雙環烷氧基、（C ₇-C ₁₄）三環烷氧基、（C ₆-C ₁₀）芳氧基、（C ₆-C ₁₀）芳基（C ₁-C ₆）烷氧基、全氟（C ₆-C ₁₀）芳氧基及全氟（C ₆-C ₁₀）芳基（C ₁-C ₃）烷氧基之群組，或者 R ₁及R ₂中的一個和R ₃及R ₄中的一個與該等所結合之碳原子一同形成經取代或未經取代之可以具有一個以上雙鍵的（C ₅-C ₁₄）環、（C ₅-C ₁₄）雙環或（C ₅-C ₁₄）三環； b）有機鈀化合物，其選自包括如下之群組： 雙（三苯膦）二氯化鈀（II）； 雙（三苯膦）二溴化鈀（II）； 雙（三苯膦）二乙酸鈀（II）； 雙（三苯膦）雙（三氟乙酸）鈀（II）； 雙（三環己基膦）二氯化鈀（II）； 雙（三環己基膦）二溴化鈀（II）； 雙（三環己基膦）二乙酸鈀（II）（Pd785）； 雙（三環己基膦）雙（三氟乙酸）鈀（II）（Pd893）； 雙（三環己基膦）雙（三氟甲磺酸）鈀（II）（Pd965）； 雙（三對甲苯基膦）二氯化鈀（II）； 雙（三對甲苯基膦）二溴化鈀（II）； 雙（三對甲苯基膦）二乙酸鈀（II）； 雙（三對甲苯基膦）雙（三氟乙酸）鈀（II）； 乙基己酸鈀（II）； 二氯雙（苄腈）鈀（II）； 氯化鉑（II）； 溴化鉑（II）；及 雙（三苯膦）二氯化鉑； c）活化劑，其選自包括如下之群組： 四氟硼酸鋰； 三氟甲磺酸鋰； 四（五氟苯基）硼酸鋰； 四（五氟苯基）硼酸鋰乙醚錯合物（LiFABA）； 四（五氟苯基）硼酸鈉乙醚錯合物（NaFABA）； 四（五氟苯基）硼酸三苯甲酯乙醚錯合物（tritylFABA）； 四（五氟苯基）硼酸鋽乙醚錯合物（tropyliumFABA）； 四（五氟苯基）硼酸鋰異丙醇錯合物； 四苯基硼酸鋰； 四（3,5-雙（三氟甲基）苯基）硼酸鋰； 四（2-氟苯基）硼酸鋰； 四（3-氟苯基）硼酸鋰； 四（4-氟苯基）硼酸鋰； 四（3,5-二氟苯基）硼酸鋰； 六氟磷酸鋰； 六苯基磷酸鋰； 六（五氟苯基）磷酸鋰； 六氟砷酸鋰； 六苯基砷酸鋰； 六（五氟苯基）砷酸鋰； 六（3,5-雙（三氟甲基）苯基）砷酸鋰； 六氟銻酸鋰； 六苯基銻酸鋰； 六（五氟苯基）銻酸鋰； 六（3,5-雙（三氟甲基）苯基）銻酸鋰； 四（五氟苯基）鋁酸鋰； 三（九氟聯苯）氟鋁酸鋰； （辛氧基）三（五氟苯基）鋁酸鋰； 四（3,5-雙（三氟甲基）苯基）鋁酸鋰； 甲基三（五氟苯基）鋁酸鋰；及 四（五氟苯基）硼酸二甲基苯胺（DANFABA）；以及 d）溶劑，其選自包括水、鄰-二甲苯、對-二甲苯、間-二甲苯、苯、氟苯、1,2-二氟苯、1,3-二氟苯、1,4-二氟苯、1,2,4-三氟苯、1,3,5-三氟苯、1,2,3,4-四氟苯、1,2,4,5-四氟苯、五氟苯、六氟苯、甲苯、乙苯、三氟甲苯、五氟乙苯、氯苯、硝苯、1,4-二㗁烷、二甲基乙醯胺、二甲基甲醯胺、二乙基甲醯胺、呋喃、四氫呋喃、二乙醚、二甲氧乙烷、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸戊酯、丙酮、甲基乙基酮、環戊烷、環已烷、甲基環戊烷、甲基環已烷、乙基環戊烷、乙基環已烷、二溴乙烷、二氯甲烷、氯仿、四氯甲烷、1,2-二氯乙烷及該等的任意組合的混合物。 As described in further detail below, the above-mentioned polymerizations are also well known vinyl addition polymerizations, which are generally carried out in the presence of organometallic compounds such as organopalladium compounds or organonickel compounds. Therefore, according to an embodiment of the present invention, there is provided a film-forming composition comprising: a) one or more olefin monomers of the general formula (I):

(I) where m is an integer of 0, 1 or 2;

is a single bond or a double bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, straight-chain or branched (C ₃ -C ₁₆ ) alkyl, perfluoro(C ₁ -C ₁₂ ) alkyl, (C ₃ -C ₁₂ ) cycloalkyl, (C ₆ -C ₁₂ ) bicycloalkyl, (C ₇ -C ₁₄ ) tricycloalkyl, (C ₆ -C ₁₀ )aryl, (C ₆ -C ₁₀ )aryl(C ₁ -C ₆ )alkyl, perfluoro(C ₆ -C ₁₀ )aryl, perfluoro(C ₆ -C ₁₀ ) Aryl (C ₁ -C ₆ ) alkyl, methoxy, ethoxy, straight or branched (C ₃ -C ₁₆ ) alkoxy, epoxy (C ₁ -C ₁₀ ) alkyl, epoxy (C ₁ -C ₁₀ )alkoxy(C ₁ -C ₁₀ )alkyl, epoxy(C ₃ -C ₁₀ )cycloalkyl, perfluoro(C ₁ -C ₁₂ )alkoxy, (C ₃ - C ₁₂ ) cycloalkoxy, (C ₆ -C ₁₂ ) bicycloalkoxy, (C ₇ -C ₁₄ ) tricycloalkoxy, (C ₆ -C ₁₀ ) aryloxy, (C ₆ -C ₁₀ ) ) aryl (C ₁ -C ₆ ) alkoxy group, perfluoro (C ₆ -C ₁₀ ) aryloxy group and perfluoro (C ₆ -C ₁₀ ) aryl (C ₁ -C ₃ ) alkoxy group group, or one of R ₁ and R ₂ and one of R ₃ and R ₄ together with the carbon atoms to which they are bound form a substituted or unsubstituted (C ₅ -C ₁₄ ) which may have more than one double bond ) ring, (C ₅ -C ₁₄ )bicyclic or (C ₅ -C ₁₄ )tricyclic; b) an organopalladium compound selected from the group comprising: bis(triphenylphosphine)palladium(II) chloride ; Bis(triphenylphosphine)palladium(II) dibromide; Bis(triphenylphosphine)palladium(II) diacetate; Bis(triphenylphosphine)bis(trifluoroacetic acid)palladium(II); Bis(tricyclohexyl) phosphine) palladium(II) dichloride; bis(tricyclohexylphosphine) palladium(II) dibromide; bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785); bis(tricyclohexylphosphine)bis (trifluoroacetic acid)palladium(II)(Pd893); bis(tricyclohexylphosphine)bis(trifluoromethanesulfonic acid)palladium(II)(Pd965); bis(tri-p-tolylphosphine)palladium(II) chloride ); bis(tri-p-tolylphosphine) palladium(II) dibromide; bis(tri-p-tolylphosphine) palladium(II) diacetate; bis(tri-p-tolylphosphine) bis(trifluoroacetic acid) palladium(II) ); palladium(II) ethylhexanoate; dichlorobis(benzonitrile)palladium(II); platinum(II) chloride; platinum(II) bromide; and bis(triphenylphosphine)platinum dichloride; c ) activator selected from the group comprising: lithium tetrafluoroborate; lithium trifluoromethanesulfonate; lithium tetrakis(pentafluorophenyl)borate; lithium tetrakis(pentafluorophenyl)borate Compound (LiFABA); Tetrakis (pentafluorophenyl) borate sodium ether complex (NaFABA); Tetrakis (pentafluorophenyl) borate trityl ether complex (tritylFABA); Tetrakis (pentafluorophenyl) Lithium borate complex (tropyliumFABA); Lithium tetrakis(pentafluorophenyl)borate isopropanol complex; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexa(pentafluorophenyl) phosphate; Lithium hexafluoroarsenate; Lithium hexaphenyl arsenate; Lithium hexa(pentafluorophenyl) arsenate; Hexa(3,5-bis(trifluoro) Lithium hexafluoroantimonate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexa(pentafluorophenyl)antimonate; Hexa(3,5-bis(trifluoromethyl)phenyl) Lithium antimonate; Lithium tetrakis(pentafluorophenyl) aluminate; Lithium tris(nonafluorobiphenyl) fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl) aluminate; Tetrakis(3,5-bis) (trifluoromethyl)phenyl)aluminate; lithium methyltris(pentafluorophenyl)aluminate; and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); and d) a solvent, selected Self-includes water, ortho-xylene, para-xylene, meta-xylene, benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,4-difluorobenzene 2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, Toluene, ethylbenzene, trifluorotoluene, pentafluoroethylbenzene, chlorobenzene, nitrobenzene, 1,4-dioxane, dimethylacetamide, dimethylformamide, diethylformamide, furan , tetrahydrofuran, diethyl ether, dimethoxyethane, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, cyclopentane, cyclohexane, methylcyclopentane, Methylcyclohexane, ethylcyclopentane, ethylcyclohexane, dibromoethane, dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and mixtures of any combination thereof.

Surprisingly, it has now been found that the use of suitable solvents in the compositions of the present invention not only facilitates the delivery of catalysts and activators, but also increases the shelf life of the compositions. That is, the composition of the present invention, when prepared using a suitable solvent, will maintain composition stability at ambient temperature, but the composition will render its composition stable at temperatures above ambient temperature, i.e., above 100°C, for example. The contained monomers undergo bulk polymerization instantaneously. In fact, this is one of the unsolved problems in the field of bulk polymeric compositions, where the catalyst has an inherently short shelf life, especially compared to similar solution polymerization conditions, since bulk polymeric compositions contain high concentrations of mono Therefore, it is difficult to control the polymerization rate under both thermal catalyst conditions and photocatalyst conditions.

In addition, the loss of monomer mobility that accompanies the polymerization process can lead to entrapment of residual monomers and non-volatile oligomeric components. Non-volatile oligomeric monomers include dimers, trimers, tetramers, and the like. Such oligomers also include low molecular weight cross-linking components, which can impart unwanted properties to the resulting film and/or solid form of the composition. Therefore, the presence of such low molecular weight residues may lead to lower thermal decomposition temperatures, lower glass transition temperatures (possibly due to plasticization), lower transparency, increased dielectric loss factors, and other unfavorable properties . This requires the composition to be highly reactive and requires quantitative conversion of monomers to be accomplished within minutes rather than hours as in solution polymerization.

More importantly, another problem encountered with the prior art involves the fact that most palladium compounds used as catalysts are polar and as exemplified by the various monomers of general formula (I), in most hydrophobic norbornene monomers The solubility and dispersibility are poor. This can further slow down or inhibit the bulk polymerization of the monomer of formula (I). Furthermore, as described in this specification, for example, activators or co-catalysts such as DANFABA and LiFABA described below are salts and do not dissolve or disperse in the hydrophobic norbornene monomer of the general formula (I). This also slows or inhibits bulk polymerization, as specifically shown in the comparative examples below.

Accordingly, it has now been discovered that the use of small amounts of low-boiling solvents to deliver catalysts and activators (ie, co-catalysts) can solve more than one of the above-mentioned problems that have not been solved in the art. Usually, the use of a small amount of solvent is sufficient to dissolve the catalyst component in the monomer and increase the polymerization rate and conversion rate. This further confirms that the catalyst delivery solvent can be systematically altered to alter the polymerization rate, thereby extending the shelf life of the more reactive monomers. It has now been found that the choice of solvent depends on the coordination ability of a suitable solvent for adjusting the reactivity to the transition metal. That is, the coordinating ability of the solvent can increase or decrease the reactivity of the catalyst used, see Chem. Eur. J. 2020, 26, 4350-4377. It has now been found that, as described below, solvents having a coordinating capacity index (a) less than zero (0) are more suitable for compositions of the present invention comprising hydrophobic monomers. The coordinating capacity index (a) refers to the quantity of the coordinating capacity of the solvent to the transition metal. (a) The lower the value, the lower the coordination ability. In other words, if the (a) value of the solvent is lower than zero (0), it is regarded as a non-coordinating solvent. In some embodiments, the coordinating ability index (a) of the solvent used in the composition of the present invention is about -0.1 to about -2.5. In other embodiments, the coordinating ability index (a) of the solvent used in the composition of the present invention is from about -0.2 to about -2.0. As mentioned above, the amount of solvent used is generally small. The amount of solvent used can be varied to obtain the desired result. Typically, the solvent may be used in an amount of less than 5% by weight relative to the total weight of the composition. For example, the amount of solvent used is as low as 1, 2, 3, or 4 wt%. In some embodiments, relative to the total weight of the composition, the amount of solvent used is about 5% to about 10% by weight; in other embodiments, the amount of solvent used is about 10% to about 20% by weight.

It is further understood that the compositions of the present invention can be used under both thermal and photobulk polymerization conditions. As described above, the composition is bulk polymerized under bulk thermal polymerization conditions with suitable temperature conditions, typically about 100°C, as described in further detail below. However, as detailed below, when the solvent mixture contains a small amount of water, the polymerization temperature can be significantly lower.

（乙醯丙酮） ₂鈀（Pd304）；

（六氟乙醯丙酮） ₂鈀（Pd（hfac） ₂或Pd520）；

雙（2,2,6,6-四甲基-3,5-庚二酮）鈀（II）（Pd472）；

（乙醯丙酮） ₂三-異丙基膦鈀；及

（六氟乙醯丙酮） ₂三異丙基膦鈀（Pd680）。 Likewise, the compositions of the present invention undergo bulk polymerization under actinic radiation as known in the art. In order to carry out photopolymerization, the composition usually contains an organic palladium compound described in this specification that can be activated by a photoactivator (usually a photoactivator acid generator). In some embodiments, non-limiting examples of suitable photoactivatable organopalladium compounds include the following:

(acetone acetone) ₂ palladium (Pd304);

(hexafluoroacetone acetone) ₂ palladium (Pd(hfac) ₂ or Pd520);

Bis(2,2,6,6-tetramethyl-3,5-heptanedione)palladium(II) (Pd472);

(acetone acetone) ₂ tri-isopropylphosphine palladium; and

(hexafluoroacetone acetone) ₂ triisopropylphosphine palladium (Pd680).

四-五氟苯基硼酸甲苯基枯基錪鎓為Elkem Silicones公司的註冊商標Bluesil PI 2074®的市售品；

（六氟）磷酸[4-（辛氧基）苯基]-苯基錪鎓（OPPI PF ₆）；

（六氟）銻酸[4-（辛氧基）苯基]-苯基錪鎓（OPPI SbF ₆）；

四（全氟苯基）硼酸（4-乙基苯基）（4-異丙基苯基）錪鎓；

三（三氟甲磺醯基）甲烷二-（對三級丁基苯基）錪鎓；

全氟-1-丁烷磺酸雙（4-三級丁基苯基）錪鎓；

對甲苯磺酸雙（4-三級丁基苯基）錪鎓；

三氟甲磺酸雙（4-三級丁基苯基）錪鎓；

其中，R ₄₂及R ₄₃相同或不同，並且各自獨立地選自直鏈或支鏈（C ₁₀-C ₁₃）烷基（例如，二苯基-4,4’-二-C _10-C ₁₃-烷基錪鎓衍生物、四（2,3,4,5,6-五氟苯基）硼酸鹽以註冊商標SILCOLEASE UV CATA 243市售；及

氯化二苯基錪鎓。 Suitable photoacid generators that can be used without any limitation include the following:

Tolycumyl iodonium tetra-pentafluorophenyl borate is a commercially available product under the registered trademark Bluesil PI 2074® of Elkem Silicones;

(hexafluoro)phosphate [4-(octyloxy)phenyl]-phenyl iodonium (OPPI PF ₆ );

(Hexafluoro)antimonate [4-(octyloxy)phenyl]-phenyl iodonium (OPPI SbF ₆ );

(4-ethylphenyl)(4-isopropylphenyl) iodonium tetrakis(perfluorophenyl)boronic acid;

Tris(trifluoromethanesulfonyl)methanedi-(p-tertiarybutylphenyl)indonium;

bis(4-tertiarybutylphenyl) iodonium perfluoro-1-butanesulfonate;

Bis(4-tertiary butylphenyl) iodonium p-toluenesulfonate;

Bis(4-tert-butylphenyl) iodonium trifluoromethanesulfonate;

wherein R ₄₂ and R ₄₃ are the same or different, and are each independently selected from linear or branched (C ₁₀ -C ₁₃ ) alkyl (eg, diphenyl-4,4'-di-C ₁₀ -C ₁₃ ) - alkyl iodonium derivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borate, commercially available under the registered trademark SILCOLEASE UV CATA 243; and

Diphenyl iodonium chloride.

為單鍵或雙鍵； R ₁、R ₂、R ₃及R ₄相同或不同，並且各自獨立地選自包括氫、直鏈或支鏈（C ₄-C ₁₆）烷基、（C ₃-C ₁₀）環烷基、（C ₃-C ₁₀）環烯基、（C ₆-C ₁₂）雙環烷基、（C ₆-C ₁₂）芳基及（C ₆-C ₁₂）芳基（C ₁-C ₆）烷基之群組；或者 R ₁及R ₂中的一個和R ₃及R ₄中的一個與該等所結合之碳原子一同形成經取代或未經取代之可以具有一個以上雙鍵的（C ₅-C ₈）環、（C ₇-C ₁₀）雙環。 在另一些實施形態中，通式（I）的疏水性單體中， m為0；

為單鍵； R ₁、R ₂、R ₃及R ₄相同或不同，並且各自獨立地選自包括氫、正丁基、正己基、環己基、環己烯基及降莰基之群組。 Therefore, the hydrophobic monomer of general formula (I) is defined as one, wherein m is 0 or 1;

is a single bond or a double bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are independently selected from the group consisting of hydrogen, straight or branched chain (C ₄ -C ₁₆ ) alkyl, (C ₃ - C ₁₀ ) cycloalkyl, (C ₃ -C ₁₀ ) cycloalkenyl, (C ₆ -C ₁₂ ) bicycloalkyl, (C ₆ -C ₁₂ ) aryl and (C ₆ -C ₁₂ ) aryl (C 6 -C 12 ) aryl groups ₁ -C ₆ ) group of alkyl groups; or one of R ₁ and R ₂ and one of R ₃ and R ₄ together with the carbon atoms to which they are bound form, substituted or unsubstituted, may have more than one (C ₅ -C ₈ ) ring of double bond, (C ₇ -C ₁₀ ) bicyclic ring. In other embodiments, in the hydrophobic monomer of general formula (I), m is 0;

is a single bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl and norbornyl.

， 下述通式的經取代或未經取代之萘基：

， 下述通式的經取代或未經取代之聯三苯：

， 下述通式的經取代或未經取代之蒽基：

， 下述通式的經取代或未經取代之茀基：

； The aryl group defined in the general formula (I) can include various aromatic groups known in the art. For example, an aryl group can be a substituted or unsubstituted biphenyl of the general formula:

, a substituted or unsubstituted naphthyl group of the following general formula:

, a substituted or unsubstituted triphenyl of the following general formula:

, substituted or unsubstituted anthracenyl of the following general formula:

, a substituted or unsubstituted perylene group of the following general formula:

;

wherein Rx at each occurrence _is independently selected from methyl, ethyl, linear or branched (C3 _{- C12} )alkyl or ( _C6 - _C10 )aryl.

The monomers of general formula (I) described in this specification are documented in the literature, or can be prepared by any method known to those skilled in the art to produce such or similar types of monomers.

（A1） 其中， b為2～6的整數； Z為鍵或R ₉R ₁₀SiOSiR ₁₁R ₁₂，其中各R ₉、R ₁₀、R ₁₁及R ₁₂相同或不同，並且各自獨立地選自包括甲基、乙基及直鏈或支鏈（C ₃-C ₆）烷基之群組； R ₅、R ₆、R ₇及R ₈相同或不同，並且各自獨立地選自包括氫、甲基、乙基及直鏈或支鏈（C ₃-C ₁₆）烷基之群組；及 通式（A2）的化合物：

（A2） 其中， R ₁₃、R ₁₄、R ₁₅及R ₁₆相同或不同，並且各自獨立地選自包括氫、甲基、乙基及直鏈或支鏈（C ₃-C ₁₆）烷基之群組；及 通式（A3）的化合物：

（A3） 其中， L為鍵或者二價連結基或間隔基，其選自： 亞甲基、伸乙基、直鏈或支鏈（C ₃-C ₁₆）伸烷基、（C ₃-C ₁₆）環伸烷基、（C ₅-C ₈）雜環、（C ₆-C ₁₂）亞芳基、（C ₅-C ₁₂）雜亞芳基及-（CH ₂） _cO（CH ₂） _c-，其中c為1～6的整數，各CH ₂可以被甲基、乙基、直鏈或支鏈（C ₃-C ₁₆）烷基及（C ₆-C ₁₂）芳基取代，其中亞甲基、伸乙基或（C ₃-C ₁₆）伸烷基中的氫部分可以被選自包括氟、三氟甲基、五氟乙基及直鏈或支鏈全氟（C ₃-C ₁₆）烷基之群組中之基團取代； R ₁₇及R ₁₈相同或不同，並且各自獨立地選自甲基、乙基、直鏈或支鏈（C ₃-C ₁₂）烷基、（C ₆-C ₁₂）芳基及（C ₆-C ₁₂）芳基（C ₁-C ₁₂）烷基，其中甲基、乙基或（C ₃-C ₁₂）烷基中的氫部分可以被選自包括氟、三氟甲基、五氟乙基及直鏈或支鏈（C ₃-C ₁₂）全氟烷基之群組中之基團取代； Ar ₁及Ar ₂相同或不同，並且各自獨立地選自可以被選自（C ₁-C ₄）烷基、（C ₁-C ₄）烷氧基、（C ₆-C ₁₀）芳基、（C ₆-C ₁₂）芳氧基、（C ₆-C ₁₂）芳基（C ₁-C ₄）烷基及（C ₆-C ₁₂）芳基（C ₁-C ₄）烷氧基中的基團取代之（C ₆-C ₁₂）亞芳基或（C ₆-C ₁₂）雜亞芳基。 As described above, the composition of the present invention may further comprise at least one polyfunctional monomeric compound. Also, it is an optional component of the composition of the present invention. Any polyfunctional monomer compound capable of promoting the formation of a three-dimensional crosslinked structure can be used in the present invention. In some embodiments, such multifunctional monomeric compounds that can be used are bifunctional monomeric compounds. Non-limiting examples of such bifunctional monomeric compounds that can be used include the following: Compounds of general formula (A1):

(A1) wherein, b is an integer from 2 to 6; Z is a bond or R ₉ R ₁₀ SiOSiR ₁₁ R ₁₂ , wherein each of R ₉ , R ₁₀ , R ₁₁ and R ₁₂ is the same or different, and is independently selected from the group consisting of the group of methyl, ethyl and straight or branched (C3 _{- C6} )alkyl _{; R5} , R6, _R7 and _R8 are the same or different, and are each independently selected from the group consisting of hydrogen, methyl , ethyl and linear or branched (C ₃ -C ₁₆ ) alkyl groups; and compounds of general formula (A2):

(A2) wherein, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different, and are each independently selected from the group consisting of hydrogen, methyl, ethyl and straight or branched (C ₃ -C ₁₆ ) alkyl groups group; and compounds of general formula (A3):

(A3) wherein, L is a bond or a divalent linking group or a spacer group, which is selected from the group consisting of: methylene, ethylidene, straight-chain or branched (C ₃ -C ₁₆ ) alkylene, (C ₃ -C ) ₁₆ ) Cycloalkylene, (C ₅ -C ₈ ) heterocycle, (C ₆ -C ₁₂ ) arylene, (C ₅ -C ₁₂ ) heteroarylene and -(CH ₂ ) _c O(CH ₂ ) _c -, wherein c is an integer from 1 to 6, and each CH ₂ may be substituted by methyl, ethyl, straight or branched (C ₃ -C ₁₆ ) alkyl and (C ₆ -C ₁₂ ) aryl groups, wherein the hydrogen moiety in methylene, ethylidene or (C ₃ -C ₁₆ )alkylene may be selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched perfluoro(C ₃ -C ₁₆ ) group substitution of alkyl groups; R ₁₇ and R ₁₈ are the same or different, and are each independently selected from methyl, ethyl, linear or branched (C ₃ -C ₁₂ ) alkyl , (C ₆ -C ₁₂ ) aryl and (C ₆ -C ₁₂ ) aryl(C ₁ -C ₁₂ ) alkyl groups, wherein the hydrogen moiety in methyl, ethyl or (C ₃ -C ₁₂ ) alkyl groups may be substituted by a group selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched (C ₃ -C ₁₂ ) perfluoroalkyl; Ar ₁ and Ar ₂ are the same or different , and are independently selected from (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₂ ) aryl (C ₆ -C ₁₂ ) aryl (C ₁ -C ₄ ) alkyl and (C ₆ -C ₁₂ ) aryl (C ₁ -C ₄ ) alkoxy groups substituted (C ₆ ) -C ₁₂ ) arylene or (C ₆ -C ₁₂ )heteroarylene.

Wherein the film formed from the composition has a dielectric constant (Dk) of less than 2.4 at a frequency of 10 GHz, a glass transition temperature of greater than 150°C, and a coefficient of thermal expansion (CTE) of less than 150 ppm/K.

It should be noted that the compositions of the present invention can be bulk polymerized under suitable temperature conditions. That is, usually, one or more monomers of the general formula (I), one or more compounds of the general formula (A1) or (A2) or (A3) as needed, the solvent described in this specification, at least one organic When the composition of the present invention of the palladium compound and the activator described in this specification is heated to a specific temperature, the composition will undergo bulk polymerization to form a solid product. Any temperature conditions capable of such bulk polymerization can be used in this specification. In some embodiments, the compositions of the present invention are heated to a temperature of about 60°C to about 150°C for a sufficient period of time, eg, about 1 hour to 8 hours. In other embodiments, the composition of the present invention is heated to about 90°C to about 130°C for a sufficient period of time, such as about 1 hour to 4 hours. As mentioned above, the organopalladium compound and activator used to effect bulk polymerization are dissolved in the specified solvent or soluble in the monomers used to form a homogeneous solution. The solution thus formed is mixed with one or more monomers of general formula (I) and, as required, a compound of general formula (A1) or (A2) or (A3) to form a homogeneous solution. Such bulk polymerization methods are well known and any procedure known to those skilled in the art can be used in this specification to form the films of the present invention. For example, see US Patent No. 6,825,307, the relevant portions of which are incorporated herein by reference.

為單鍵； R ₁、R ₂、R ₃及R ₄相同或不同，並且各自獨立地選自包括氫、正丁基、正己基、環己基、環己烯基及降莰基之群組。 In some embodiments, the film-forming composition comprises a monomer of general formula (I), wherein m is 0;

is a single bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl and norbornyl.

雙環[2.2.1]庚-2-烯（降莰烯或NB）；

雙環[2.2.1]庚-2,5-二烯（降莰二烯或NBD）；

5-丁基雙環[2.2.1]庚-2-烯（BuNB）；

5-己基雙環[2.2.1]庚-2-烯（HexNB）；

5-辛基雙環[2.2.1]庚-2-烯（OctNB）；

5-癸基雙環[2.2.1]庚-2-烯（DecNB）；

5-乙烯基雙環[2.2.1]庚-2-烯（VNB）；

5-亞乙基雙環[2.2.1]庚-2-烯（ENB）；

5-（丁-3-烯-1-基）雙環[2.2.1]庚-2-烯（ButenylNB）；

5-（己-5-烯-1-基）雙環[2.2.1]庚-2-烯（HexenylNB）；

5-環己基雙環[2.2.1]庚-2-烯（CyHexNB）；

5-（環己-3-烯-1-基）雙環[2.2.1]庚-2-烯（CyclohexeneNB）；

5-苯基雙環[2.2.1]庚-2-烯（PhNB）；

5-苯乙基雙環[2.2.1]庚-2-烯（PENB）；

2,2’-二（雙環[2.2.1]庚烷-5-烯）（NBANB）；

1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘，亦稱為四環十二碳烯（TD）；

2-己基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘（HexTD）；

1,4,4a,5,8,8a-六氫-1,4:5,8-二甲橋萘（TDD）；

3a,4,7,7a-四氫-1H-4,7-甲橋茚（DCPD）；

3a,4,4a,5,8,8a,9,9a-八氫-1H-4,9:5,8-二甲橋環戊[b]萘（CPD3）；

5-（芐氧基）雙環[2.2.1]庚-2-烯；

5-（2-（[1,1’-聯苯]-2-基氧基）乙基）雙環[2.2.1]庚-2-烯（NBEtOPhPh）；

5-（2-（[1,1’-聯苯]-2-基氧基）乙基）雙環[2.2.1]庚-2-烯（NBEtO-2-PhPh）；

5-降莰烯基甲基丁香酚乙酸酯（EuAcNB）；

5-降莰烯基甲基丁香酚（EuOHNB）；

（雙環[2.2.1]庚-5-烯-2-基甲氧基）（甲基）二苯基矽烷（NBCH ₂OSiMePh ₂）；

（雙環[2.2.1]庚-5-烯-2-基甲氧基）（乙基）二苯基矽烷；

（雙環[2.2.1]庚-5-烯-2-基甲氧基）（乙基）（甲基）（苯基）矽烷；

（雙環[2.2.1]庚-5-烯-2-基甲氧基）二甲基（苯基）矽烷；

雙環[2.2.1]庚-5-烯-2-基三甲氧基矽烷（TMSNB）；

雙環[2.2.1]庚-5-烯-2-基三乙氧基矽烷（NBSi（OC ₂H ₅） ₃）；

雙環[2.2.1]庚-5-烯-2-基（三級丁氧基）二甲氧基矽烷；

（2-（雙環[2.2.1]庚-5-烯-2-基）乙基）三甲氧基矽烷；

NB（MeOH） ₂；

PhAcNB；

5-（苯氧基甲基）雙環[2.2.1]庚-2-烯（NBMeOPh）；

5-（（[1,1’-聯苯]-2-基氧基）甲基）雙環[2.2.1]庚-2-烯（NBMeOPhPh）；

2-苯基-四環十二碳烯（PhTD）；

2-苄基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘；

2-苯乙基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘（PETD）；

2-丁基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘（ButylTD）；

2-己基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘（HexylTD）；

2-辛基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘（OctylTD）；

2-癸基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘（DecylTD）；

2-環己基-四環十二碳烯（CyclohexylTD）；

2-環己基甲基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘；

2-環己基乙基-1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘；及

（1,2,3,4,4a,5,8,8a-八氫-1,4:5,8-二甲橋萘-2-基）乙酸甲酯（TDMeOAc）。 Also, any monomer of the general formula (I) can be used to form the film-forming composition of the present invention. Non-limiting examples of monomers of general formula (I) are selected from the group comprising:

Bicyclo[2.2.1]hept-2-ene (norbornene or NB);

Bicyclo[2.2.1]hept-2,5-diene (norbornadiene or NBD);

5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);

5-Octylbicyclo[2.2.1]hept-2-ene (OctNB);

5-Decylbicyclo[2.2.1]hept-2-ene (DecNB);

5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

5-ethylenebicyclo[2.2.1]hept-2-ene (ENB);

5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB);

5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);

5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB);

5-phenylbicyclo[2.2.1]hept-2-ene (PhNB);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

2,2'-bis(bicyclo[2.2.1]heptane-5-ene) (NBANB);

1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene, also known as tetracyclododecene (TD);

2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD);

1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene (TDD);

3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD);

3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3);

5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

5-(2-([1,1'-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh);

5-(2-([1,1'-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtO-2-PhPh);

5-Norbornylmethyleugenol acetate (EuAcNB);

5-Norbornylmethyleugenol (EuOHNB);

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (NBCH ₂ OSiMePh ₂ );

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

Bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB);

Bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSi(OC ₂ H ₅ ) ₃ );

Bicyclo[2.2.1]hept-5-en-2-yl(tertiary butoxy)dimethoxysilane;

(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane;

NB(MeOH) ₂ ;

PhAcNB;

5-(phenoxymethyl)bicyclo[2.2.1]hept-2-ene (NBMeOPh);

5-(([1,1'-biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene (NBMeOPhPh);

2-Phenyl-tetracyclododecene (PhTD);

2-benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene;

2-Phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (PETD);

2-Butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (ButylTD);

2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexylTD);

2-Octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (OctylTD);

2-Decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (DecylTD);

2-cyclohexyl-tetracyclododecene (CyclohexylTD);

2-Cyclohexylmethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene;

2-Cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene; and

Methyl (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalen-2-yl)acetate (TDMeOAc).

1,3-雙（2-（雙環[2.2.1]庚-5-烯-2-基）乙基）-1,1,3,3-四甲基二矽氧烷（NBC2DMSC2NB）；及

1,4-二（雙環[2.2.1]庚-5-烯-2-基）丁烷（NBC4NB）。 Likewise, any specific example within the scope of the general formula (A1) that brings the intended effect can be used for the film-forming composition of the present invention. Non-limiting examples of compounds of general formula (A1) are selected from the group comprising:

1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB); and

1,4-Bis(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBC4NB).

1,4,4a,4b,5,8,8a,8b-八氫-1,4:5,8-二甲橋伸聯苯基（（NBD）2）。 Any specific example within the range of the general formula (A2) that brings the intended effect can be used for the film-forming composition of the present invention. Non-limiting examples of compounds of general formula (A2) are:

1,4,4a,4b,5,8,8a,8b-Octahydro-1,4:5,8-Dimethylbiphenyl ((NBD)2).

3,3’-（（氧代雙（亞甲基））雙（4,1-伸苯基））雙（3-（三氟甲基）-3H-二氮環丙烯）；

4,4’’-雙（3-（三氟甲基）-3H-二氮環丙烯-3-基）-1,1’:3’,1’’-聯三苯；

3,5-雙（4-（3-（三氟甲基）-3H-二氮環丙烯-3-基）苯基）吡啶；

3,3’-（（全氟丙烷-2,2-二基）雙（[1,1’-聯苯]-4’,4-二基））雙（3-（三氟甲基）-3H-二氮環丙烯）；及

3,3’-（（全氟丙烷-2,2-二基）雙（4,1-伸苯基））雙（3-（三氟甲基）-3H-二氮環丙烯），由XLynX Materials,Inc銷售之市售品GEN-I BondLynx。 Finally, any specific example within the range of the general formula (A3) that brings the desired effect can be used for the film-forming composition of the present invention. Non-limiting examples of compounds of general formula (A3) are:

3,3'-((oxobis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazacyclopropene);

4,4''-bis(3-(trifluoromethyl)-3H-diazacyclopropen-3-yl)-1,1':3',1''-bitriphenyl;

3,5-bis(4-(3-(trifluoromethyl)-3H-diazacyclopropen-3-yl)phenyl)pyridine;

3,3'-((Perfluoropropane-2,2-diyl)bis([1,1'-biphenyl]-4',4-diyl))bis(3-(trifluoromethyl)- 3H-diazacyclopropene); and

3,3'-((Perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazacyclopropene), by XLynX Commercially available GEN-I BondLynx sold by Materials, Inc.

As described above, the film-forming composition according to the present invention contains at least one monomer of the general formula (I) and optionally at least one compound of the general formula (A1) or (A2) or (A3). The monomers of general formula (I) and the compounds of general formula (A1) or (A2) or (A3) used to form the compositions of the present invention can be used in any amount that brings about the desired effects, including those described in this specification. The low dielectric properties and/or thermal/mechanical properties or both are described, or other desired properties depending on the intended end application. Therefore, the molar ratio of the monomer of the general formula (I) to the compound of the general formula (A1) or (A2) or (A3) may be 100:0 to 90:10. In some embodiments, the molar ratio of the monomer of general formula (I): the compound of general formula (A1) or (A2) or (A3) is in the range of 99:1 to 95:5, in other embodiments In the form, the molar ratio is 98:2 to 91:9, 97:3 to 92:8, 96:4 to 93:7, and the like.

It should be further noted that one or more monomers of general formula (I) and one or more compounds of general formula (A1) or (A2) or (A3) can also be used in the compositions of the present invention. Therefore, the molar ratio of the first monomer of the general formula (I) to the second monomer of the general formula (I) may be 1:99 to 99:1. In some embodiments, the molar ratio of the first monomer of general formula (V): the second monomer of general formula (V) is in the range of 5:95 to 95:5; in other embodiments, The molar ratios are 10:90 to 90:10, 15:85 to 85:15, 20:80 to 80:20, 0:70 to 70:30, 60:40 to 40:60, and 50:50. Likewise, when more than one monomer of general formula (I) is used in the composition of the present invention, one or more compounds of general formula (A1) or (A2) or (A3) can be used in any desired amount, including this specification proportions recorded in.

Generally, the composition according to the present invention contains one or more monomers of the general formula (I) above, and as described below, the composition of various embodiments can be selected to impart properties required for the intended use to the embodiment, whereby the Various specific applications adjust the implementation form. Thus, in some embodiments, the compositions of the present invention comprise more than two different monomers of general formula (I), such as three different monomers of general formula (I) or four different monomers of general formula (I) and any desired amount of a compound of general formula (A1) or (A2) or (A3).

For example, by employing appropriate combinations of different monomers of general formula (I), as described above, compositions having desired low dielectric properties, thermomechanical properties, and other properties can be prepared. In addition, as further described below, it is preferred to include other polymeric materials or monomeric materials suitable to provide low loss and low dielectric properties depending on the end application.

Even further advantageously, it has now been found that by using more than one compound of the general formula (A1) or (A2) or (A3), it is possible to form a cross-linked structure in the polymer backbone. That is, crosslinking can occur intramolecularly (ie, between two crosslinkable sites on the same polymer chain). This is statistically possible and all such combinations are part of the present invention. By forming such intermolecular or intramolecular crosslinks, polymers formed from the compositions of the present invention provide a property that has heretofore been unavailable. This can include, for example, improved thermal properties. That is, the glass transition temperature is much higher than that observed for non-crosslinked polymers of similar composition. Additionally, such cross-linked polymers are more stable at high temperatures, which may be higher than 350°C. High temperature stability can also be determined by thermogravimetric analysis (TGA) methods known in the art. One such determination includes a temperature at which the polymer loses 5% of its weight (T _d5 ). As shown in the following specific examples, the T _d5 of the polymer formed from the composition of the present invention described below is usually in the range of about 270°C to about 320°C or higher. In some embodiments, the T _d5 of polymers formed from the compositions of the present invention is in the range of about 280°C to about 300°C.

It should be further noted that it is not always necessary to use more than one compound of the general formula (A1) or (A2) or (A3) in order to achieve cross-linking of the polymer formed from the composition. That is, as described above, when the monomer of general formula (I) contains more than one different monomer with unsaturated double bonds, the monomer itself can be used for intermolecular crosslinking or intramolecular crosslinking with other polymer chains. of the monomer. Accordingly, in some embodiments, there is provided a composition comprising at least two monomers of general formula (I), wherein at least one of the monomers comprises a double bond. Any such combination is part of the present invention.

Additionally, it should be noted that the crosslinked polymers formed from the compositions of the present invention can form thermosets, thus providing additional advantages, especially in certain applications where thermoplasticity is not required. For example, thermoplastic polymers are less desirable in any application involving high temperatures because such polymeric materials flow and are not suitable for such temperature applications. Such applications include millimeter wave radar antennas and others contemplated in this specification.

Advantageously, as described below, the compositions according to the present invention are capable of forming films. The films thus formed from the compositions of the present invention exhibit hitherto unattainable combinations of low dielectric properties and very high glass transition temperatures, among other improved properties. Thus, in some embodiments, films formed from the compositions of the present invention have a dielectric constant (Dk) of 2.0 to 2.38 at a frequency of 10 GHz, a glass transition temperature of about 160°C to about 350°C, and about 100 ppm/K ~ Coefficient of Thermal Expansion (CTE) of ~140ppm/K. In other embodiments, films formed from the compositions of the present invention have a dielectric constant (Dk) of 2.10 to 2.30 at a frequency of 10 GHz, a glass transition temperature of about 190°C to about 350°C, and a glass transition temperature of about 100 ppm/K to about 100 ppm/K. Coefficient of Thermal Expansion (CTE) of about 140ppm/K. In still other embodiments, films formed from the compositions of the present invention have a glass transition temperature of from about 220°C to about 350°C or higher.

Advantageously, it has further been found that the low dielectric properties of films formed from the compositions of the present invention can be improved by adding more than one filler material. The filler material can be an organic material or an inorganic material. Any known filler material that brings the desired effect can be used in this specification.

Accordingly, in some embodiments, the film-forming compositions according to the present invention comprise inorganic fillers. Suitable inorganic fillers have a lower coefficient of thermal expansion (CTE) than the films formed from the compositions of the present invention. Non-limiting examples of such inorganic fillers include: oxides, such as silica, alumina, diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, metal ferrites; hydroxides, such as hydroxide Aluminum, magnesium hydroxide; calcium carbonate (light and heavy); magnesium carbonate, dolomite; carbonates such as doronite; sulfates such as calcium sulfate, barium sulfate, ammonium sulfate and calcium sulfite; talc, mica; clays ; glass fibers; calcium silicates; montmorillonite; silicates, such as bentonite; borates, such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate; carbon black; carbon, such as carbon fiber; iron powder ; copper powder; aluminum powder; zinc oxide; molybdenum disulfide; boron fiber; potassium titanate; and lead zirconate.

In other embodiments, the film-forming composition according to the present invention further comprises an organic filler, which is usually a synthetic resin in powder form or other suitable form or polymer form. Examples of such polymeric fillers include, without limitation, poly(α-methylstyrene), poly(vinyl-toluene), copolymers of α-methylstyrene and vinyl-toluene, and the like. Examples of such polymer filler powders further include various thermosetting or thermoplastic resins, such as alkyd resins, epoxy resins, silicone resins, phenolic resins, polyesters, acrylic and methacrylic resins, acetal resins, polyethylene , polyether, polycarbonate, polyamide, polysiloxane, polystyrene, polyvinyl chloride, fluororesin, polypropylene, ethylene-vinyl acetate copolymers, and powders of copolymers of these resins. Other examples of organic fillers include aromatic or aliphatic polyamide fibers, polypropylene fibers, polyester fibers, aramid fibers, and the like.

In some embodiments, the filler is an inorganic filler. Therefore, the thermal expansion coefficient can be effectively reduced. In addition, heat resistance can be improved. Therefore, in some embodiments, the inorganic filler is silica. Therefore, the thermal expansion coefficient is lowered while improving the dielectric properties. Various forms of silica fillers are known in the art, and all such suitable silica fillers can be used in the compositions of the present invention. Examples of such silica fillers include, but are not limited to, fused silica, including fused spherical silica and fused crushed silica, crystalline silica, and the like. In some embodiments, the filler used is fused silica. Advantageously, it has now been found that by using spherical silica, it is possible to form compositions containing maximum loadings, which can be as high as 80% by weight. Particularly excellent dielectric properties can be achieved by using a suitable silica filler. Typically, the amount of filler material can range from about 5 wt % to more than 80 wt %. In some embodiments, as described in this specification, when the polymerization is performed to form the film/sheet, the content of the filler in the composition is about 30-80% by weight relative to the total solid content of the composition. By appropriately adjusting the content of the filler, the balance between the dielectric properties and the thermal expansion coefficient can be improved. In other embodiments, the content of the filler in the composition is about 40-70% by weight relative to the total solid content of the composition.

Usually, the filler is treated with a silane compound having an alkoxysilyl group and an organic functional group such as an alkyl group, an epoxy group, a vinyl group, a phenyl group and a styryl group in one molecule. Examples of such silane compounds include: silanes having alkyl groups such as ethyltriethoxysilane, propyltriethoxysilane or butyltriethoxysilane (alkylsilane); phenyltriethoxysilane , benzyl triethoxy silane or phenethyl triethoxy silane and other silanes having phenyl groups; styrene trimethoxy silane, butenyl triethoxy silane, propenyl triethoxy silane or vinyl Silane with styryl group such as trimethoxysilane (vinylsilane); silane with acryl or methacryl group such as γ-(methacryloyloxypropyl)trimethoxysilane; Silane with amino groups such as triethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; Or epoxy groups such as γ-(3,4-epoxycyclohexyl)ureidotriethoxysilane, etc. A silane having a mercapto group such as γ-mercaptopropyltrimethoxysilane can also be used. It should be further noted that more than one of the above-mentioned silane compounds can be used in any combination.

It should be further noted that when inorganic fillers are used as fillers, the fillers are usually treated with "non-polar silane compounds". Therefore, the adhesiveness between the cycloolefin polymer formed from the composition of the present invention and the filler can be improved. As a result, the mechanical properties of the molded body can be improved. Advantageously, it has now been found that by treating with "non-polar silane compounds" the adverse effects on dielectric properties can be eliminated or reduced. The "non-polar silane compound" used in this specification refers to a silane compound having no polar substituent. Polar substituents represent groups capable of hydrogen bonding or ionic dissociation. Such polar substituents include, but are not limited to, -OH, -COOH, -COOM, NH ₃ , NR ₄ ⁺ A ^- , -CONH ₂ , and the like. Wherein, M is a cation, such as alkali metal, alkaline earth metal or quaternary ammonium salt; R is H or an alkyl group with 8 or less carbon atoms; A is an anion, such as a halogen atom.

In some embodiments, the surface of the filler is modified with vinyl. The use of vinyl groups is advantageous because vinyl groups are non-polar substituents that provide much-needed low dielectric properties. For example, vinyl silanes can be used to modify the surface of the filler with vinyl. Specific examples of vinylsilane are described in this specification.

Typically, the average particle size of the filler used is in the range of about 0.1 to 10 [mu]m. In some embodiments, the average particle size is about 0.3-5 μm, and in other embodiments, the average particle size is about 0.5-3 μm. The mean particle size is defined as the mean diameter of the particles as determined by light scattering. When more than one type of filler is used, the average particle size of more than one such filler remains within the above numerical ranges. Since the average particle size of the filler is appropriately small, the specific surface area of the filler is reduced. As a result, the number of polar functional groups that may adversely affect the dielectric properties is reduced, and the dielectric properties are easily improved. In addition, since the average particle diameter of the filler is appropriately small, it is easy to polymerize and form a film from the composition of the present invention. More importantly, the films/sheets so formed exhibit uniform thickness and flatness that is highly desirable in the intended application.

The composition of the present invention may contain components other than the above-mentioned components. Components other than the above-mentioned components include coupling agents, flame retardants, mold release agents, antioxidants, and the like. Non-limiting examples of coupling agents include vinyl silanes, acrylic and methacrylic silanes, styryl silanes, silane coupling agents such as isocyanato silanes, and the like. By using the silane coupling agent, the adhesiveness between the composition of the present invention and the matrix material and the like can be improved.

Non-limiting examples of flame retardants include phosphorus-based flame retardants such as tricresyl phosphate, dimethyl phosphate, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10 - Phosphophenanthrene-10-oxide; halogen-based flame retardants, such as brominated epoxy resins; and inorganic flame retardants, such as aluminum hydroxide and magnesium hydroxide.

The composition of the present invention may further comprise one or more compounds or additives having functions such as adhesion promoters, surface leveling agents, synergists, plasticizers, curing accelerators, free radical initiators and the like.

Surprisingly, it has now been found that by using more than one thermal radical generator, the crosslinking of polymers formed from the compositions of the present invention can be promoted, with the result that the crosslinked polymers exhibit greatly improved thermal properties. For example, both the glass transition temperature (T _g ) and the temperature at which a weight loss of 5 wt % occurs (T _d5 ) of the polymer obtained can be increased. The increase in T _g can be large, possibly in the range of about 10°C to 50°C. In some embodiments, the T _g of the polymer can be increased by 20°C to 40°C by using an appropriate amount of thermal free radical generator. Likewise, the T _d5 of the polymer may also increase by about 3°C to 10°C.

Any compound that forms free radicals when heated can be used for this purpose. Suitable generic classes of such compounds include peroxides, peroxyacids, azo compounds, N-alkoxyamines, N-oxoamines, and the like. Non-limiting examples of such specific thermal free radical generators include dibenzoyl peroxide, dicumyl peroxide (DCP), m-chloroperbenzoic acid, methyl ethyl ketone peroxide, azobisisobutylene Nitrile (AIBN), (1-phenyl-3,3-dipropyltriazene), (1-(phenyldiazenyl)pyrrolidine), (1-(phenyldiazenyl)piperidine) pyridine), (1-(phenyldiazenyl)nitrogen), etc.

Also, any suitable amount of thermal radical generator that brings the desired effect can be used in the composition of the present invention. Typically, the amount may range from about 2 pphr (parts per hundred parts resin: parts per hundred parts resin) to about 10 pphr or more. In some embodiments, the amount of photoradical generator used is from about 3 pphr to about 6 pphr.

The film-forming composition according to the present invention is selected from the group comprising: 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD), bis(tricyclohexylphosphine) palladium diacetate ( II) (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); Tetracyclododecene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine)palladium(II) diacetate (Pd785) and tetrakis(pentafluoro) phenyl) dimethylaniline borate (DANFABA); 2,2'-Bis(bicyclo[2.2.1]heptane-5-ene) (NBANB), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and tetrakis(pentafluorophenyl)boronic acid methylaniline (DANFABA); 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), bis(tricyclohexylphosphine)diacetate palladium(II) (Pd785) and tetrakis(pentafluorophenyl)boronic acid dimethylaniline (DANFABA) ); 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 2,2'-bis(bicyclo[2.2.1]heptane-5-ene) (NBANB), 1,3-bis(2- (Bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), bis(tricyclohexylphosphine)palladium diacetate (II) (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bis(tricyclohexylphosphine)bis Palladium(II) acetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); and 3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), bis(tricyclohexylphosphine) ) palladium (II) diacetate (Pd785) and dimethylaniline tetrakis (pentafluorophenyl) borate (DANFABA); 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine)diacetate palladium (II) ) (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hept-2,5- Diene (NBD), bis(tricyclohexylphosphine)diacetate palladium (II) (Pd785) and tetrakis (pentafluorophenyl) dimethylaniline borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis( Tricyclohexylphosphine) palladium (II) diacetate (Pd785) and dimethylaniline tetrakis (pentafluorophenyl) borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hept-2,5-diene (NBD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethyl tetrakis(pentafluorophenyl)borate Aniline (DANFABA); and 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a, 9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3), bis(tricyclohexylphosphine) palladium (II) diacetate (Pd785) and tetrakis(penta) Fluorophenyl) dimethylaniline borate (DANFABA).

It should be noted that the composition of the present invention can be formed in any shape or form, and is not particularly limited to a film. Thus, in some embodiments, the compositions of the present invention can be formed as sheets. The thickness of the sheet is not particularly limited, but when considering use as a dielectric material, the thickness is, for example, 0.01 to 0.5 mm. In other embodiments, the thickness is about 0.02-0.2 mm. Typically, the sheets so formed do not flow substantially at room temperature (25°C). The sheets can be provided on any carrier layer or individually. Examples of carrier layers include polyimide films. Other known peelable films can be used.

As mentioned above, the films/sheets formed in accordance with the present invention have excellent dielectric properties. Quantitatively, the relative permittivity, ie, the dielectric constant (Dk), of the film/sheet is about 2.0 to 2.38 at a frequency of 10 GHz. The dielectric loss tangent is about 0.0003-0.005 at a frequency of 10 GHz, and in other embodiments, the dielectric loss tangent is about 0.0004-0.003. As a result, the composition of the present invention can be applied to various devices requiring dielectric materials, such as antennas for millimeter-wave radars. For example, refer to JP2018-109090 and JP2003-216823. Antennas typically consist of an insulator and conductor layers (eg, copper foil). The composition or sheet of the present invention can be used as a part or the whole of an insulator. An antenna using the composition or sheet of the present invention as a part or the whole thereof has high-frequency characteristics and reliability (durability).

The conductor layer in the antenna is formed of, for example, a metal having the required conductivity. Circuits are formed on the conductor layers using known circuit fabrication methods. The conductor layer forming the conductor includes various metals having conductivity, such as gold, silver, copper, iron, nickel, aluminum or alloys thereof. As a method of forming the conductor layer, a known method can be used. Examples include vapor deposition, electroless plating, and electrolytic plating. Alternatively, metal foil (eg, copper foil) can be crimped by thermocompression bonding. The metal foil constituting the conductor layer is usually a metal foil for electrical connection. In addition to copper foil, various metal foils such as gold, silver, nickel, and aluminum can be used. The metal foil may also include substantially (eg, 98 wt % or more) alloy foil composed of these metals. Among these metal foils, copper foils are generally used. The copper foil may be rolled copper foil or electrolytic copper foil.

As described above, the compositions of the present invention are used as such to form films or sheets. However, in some embodiments, as described in this specification, the composition may contain a small amount of solvent to dissolve the catalyst. In addition, in certain applications, the composition of the present invention can also be used as a low molecular weight varnish type material. In such applications, an appropriate amount of the desired solvent can be added to maintain the solids content of the composition at about 10-70% by weight upon polymerization. Again, any solvent suitable for forming such solutions can be used as the single solvent or solvent mixture required for such applications.

In another aspect of the present invention, a kit for forming a membrane is provided. The composition of the present invention is dispensed in the kit. Therefore, in some embodiments, a kit is provided in which one or more olefin monomers of general formula (I) described in this specification, general formula (A1) or ( One or more compounds of A2) or (A3), the organic palladium compound described in this specification, and the above-mentioned activator. In some embodiments, the kits of the present invention comprise one or more monomers of general formula (I) in combination with one or more compounds of general formula (A1) or (A2) or (A3) to achieve the desired results and/or intended purpose.

In another aspect of this embodiment of the present invention, the kit of the present invention forms a polymer film only when bulk polymerized at a suitable temperature for a sufficiently long period of time. That is, as described in this specification, the composition of the present invention is cast on a surface or substrate to be encapsulated and subjected to suitable heat treatment to polymerize the monomers to form a solid polymer, which may be a film or form of the sheet.

Generally, as mentioned above, such polymerization can be carried out under various temperature conditions, for example heating can also be carried out in stages, heating to 90°C followed by heating at 110°C and finally at 150°C for a sufficient time, for example at each temperature Heating in stages for 5 minutes to 2 hours, and if necessary, further heating at temperatures above 150°C for various times, eg, 5 minutes to 15 minutes, etc. Alternatively, the polymerization can be carried out at a single temperature of about 100°C to 250°C for a sufficiently long time, eg, 1 hour to 3 hours or more. By practicing the present invention, polymer films can be obtained that are substantially uniform films on such substrates. The thickness of the film can be specified or defined as above, and can usually be 50 to 500 μm or more.

Various known heating methods for the production of sheet materials can be utilized in the production of the sheet, ensuring the flatness of the sheet and suppressing unexpected shrinkage. For example, it is possible to first heat at a relatively low temperature and then gradually increase the temperature. In order to ensure flatness and the like, heating and/or pressing with a flat plate may be performed after pressing with a flat plate (glass plate) before heating. The pressure used in such pressurization is, for example, 0.1 to 8 MPa, and in other embodiments, the pressure is in the range of about 0.3 to 5 MPa.

In some embodiments of the present invention, the kit described in this specification includes a composition comprising two or more monomers of general formula (I) described in this specification and the above-mentioned general formula (A1) or Two or more compounds of (A2) or (A3). In addition, any monomer of the general formula (I) or the compound of the general formula (A1) or (A2) or (A3) described in this specification can be used in this embodiment, and can be used according to the properties of the intended use any amount.

In some embodiments, the kits described in this specification include the various exemplary compositions described above.

In yet another aspect of the present invention, there is further provided a method of forming a film for use in the manufacture of various optoelectronic and/or automotive devices, the method comprising:

The step of forming a homogeneous and transparent composition comprising: a combination of one or more monomers of the general formula (I) and one or more compounds of the general formula (A1) or (A2) or (A3); The organopalladium compound described; the activator described in this specification; and the filler described in this specification;

the step of coating a suitable substrate with the composition or casting the composition on a suitable substrate to form a film; and

The step of heating the film to a suitable temperature to initiate the polymerization of the monomers.

The step of coating a desired substrate with the photosensitive composition of the present invention to form a film can be performed by the steps described in this specification and/or any coating steps known to those skilled in the art such as spin coating. Other suitable coating methods include, without limitation, spray coating, knife coating, meniscus coating, ink jet coating, and slot coating. The mixture can also be cast on a substrate to form a film. Suitable substrates include any suitable substrates that can be used in electrical, electronic or optoelectronic devices, such as semiconductor substrates, ceramic substrates, glass substrates.

Next, the coated substrate is baked, ie heated, to promote bulk polymerization, for example, at a temperature of 50°C to 150°C for about 1 to 180 minutes, and other suitable temperatures and times can also be used. In some embodiments, the substrate is baked at a temperature of about 100°C to about 120°C for 120 minutes to 180 minutes. In other embodiments, the substrate is baked at a temperature of about 110°C to about 150°C for 60 minutes to 120 minutes.

The electrical properties of the films thus formed were then evaluated using any method known in the art. For example, the dielectric constant (Dk) or the permittivity at a frequency of 10 GHz was measured by the cavity resonator method (manufactured by AET, conforming to JIS C 2565) using a permittivity measuring device. and dielectric loss tangent. The coefficient of thermal expansion (CTE) was measured using a thermomechanical analyzer (SS 6000, manufactured by Seiko Instruments Inc.) on a measurement sample with a size of 4 mm (width) × 40 mm (length) × 0.1 mm (thickness), and the measurement temperature was between 30 and 30 mm. In the range of 350 degreeC, the temperature increase rate is 5 degreeC/min. The coefficient of linear expansion at 50°C to 100°C was used as the coefficient of linear expansion. Generally, as described in this specification, films formed in accordance with the present invention exhibit excellent dielectric properties and can be tuned to desired dielectric properties.

Therefore, as described in this specification, in some embodiments of the present invention, a film or sheet obtained by bulk polymerization of the composition is also provided. In another embodiment, as described in this specification, there is also provided an electronic device comprising the film/sheet of the present invention.

In another aspect of the invention, it has surprisingly been found that the addition of a small amount of water to the catalyst can result in a more reactive system in which the composition polymerizes more rapidly to provide a polymer product with improved properties. Accordingly, in some embodiments of the present invention, the compositions of the present invention comprise a catalyst solution containing at least about 5% by weight of water. In other embodiments of the present invention, the composition of the present invention comprises a catalyst solution containing from about 5% to about 20% by weight of water. In other embodiments of the present invention, the composition of the present invention comprises a catalyst solution containing from about 6% to about 10% by weight of water.

As can be seen from the following specific examples, the polymerization of the composition of the present invention can be accelerated at a relatively low temperature by adding a specific amount of water to the catalyst system. That is, the polymerization initiation temperature can be lowered by 30° C. by adding about 8% by weight of water to the catalyst system. This dramatic reduction in polymerization onset temperature is shown in Figure 6, which shows a comparison of the polymerization onset temperature of a composition containing about 7.6 wt% water to that of a composition without water. It is evident that by adding water, the polymerization onset temperature was lowered by 30°C.

Advantageously, it has now been found that aging of the aqueous catalyst solution further increases the activity of the catalyst. Thus, in some embodiments of the present invention, the catalyst solution is aged for at least 10 days. In other embodiments of the present invention, the catalyst solution is aged for about 10 to 20 days. In yet other embodiments of the present invention, the catalyst solution is aged for about 14 to 18 days. It should be noted, however, that in some embodiments, the aqueous catalyst solution can be aged for less than 10 days or more than 20 days, depending on the type of catalyst used, all of which are within the scope of the present invention. within the range.

In the following examples, the preparation and use methods of some compounds/monomers, polymers and compositions of the present invention are described in detail. Specific preparation methods are within the scope of the generally described preparation methods above, and are used to illustrate such general preparation methods. The examples are for illustrative purposes only and are not intended to limit the scope of the invention. The monomer to catalyst ratios used in the examples and throughout the specification are molar ratios.

Example (General)

The following abbreviations used in this specification are used to describe some of the compounds, instruments and/or methods employed in specific embodiments of the present invention:

HexTD: 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene; TD: tetracyclododecene; BuNB: 5 - Butylbicyclo[2.2.1]hept-2-ene; PENB: 5-phenethylbicyclo[2.2.1]hept-2-ene; PhNB: 5-phenylbicyclo[2.2.1]hept-2- alkene; DecNB: 5-decylbicyclo[2.2.1]hept-2-ene; HexNB: 5-hexylbicyclo[2.2.1]hept-2-ene; NBANB: 2,2'-bis(bicyclo[2.2. 1] Heptane-5-ene; CyHexNB: 5-cyclohexylbicyclo[2.2.1]hept-2-ene; DCPD: 3a,4,7,7a-tetrahydro-1H-4,7-methylindene; NBD: bicyclo[2.2.1]hept-2,5-diene; TDD: 1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene; NBC2DMSC2NB: 1 ,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane; CPD3: 3a,4, 4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylbridgecyclopenta[b]naphthalene; Pd785: bis(tricyclohexylphosphine)diacetate palladium(II) ; DANFABA: dimethylaniline tetrakis(pentafluorophenyl)borate; DCP: dicumyl peroxide; Rhodorsil-2074: tolycumyl iodonium tetrakis-pentafluorophenyl borate; UV-CATA: diphenyl -4,4'-Di-C10-13-Alkyl iodonium derivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borate; EA: ethyl acetate; THF: tetrahydrofuran; CH : cyclohexane; MCH: methylcyclohexane; TFT: trifluorotoluene; GPC: gel permeation chromatography; _Mw : weight average molecular weight; GC: gas chromatography; DSC: differential scanning calorimetry ; TGA: thermogravimetric analysis; TMA: thermomechanical analysis; UV-VIS spectra: ultraviolet-visible spectroscopy.

Various monomers as used in this specification are commercially available or can be readily prepared following the procedures described in US Patent Application No. 9,944,818.

Examples 1 to 6

In each of Examples 1 to 6, catalyst stock solutions in sealed glass vials under nitrogen atmosphere were prepared by dissolving Pd785 (0.031 g, 0.039 mmol) in the catalyst delivery solvent (3.2 g). Example 1: THF, Examples 2 and 5: Toluene, Example 3: CH, Example 4: MCH, Example 6: TFT. A cocatalyst stock solution was prepared by dissolving DANFABA (0.176 g, 0.22 mmol) in the cocatalyst delivery solvent THF or EA (3.2 g) in a sealed glass vial under nitrogen. The desired amount of catalyst or co-catalyst solution is withdrawn with a syringe and added to the monomer. The sample HexTD (2.44 g, 9.98 mmol) was mixed with a solution of Pd785 in the desired solvent (0.07-0.08 g, 0.00098 mmol) and a solution of DANFABA in the desired solvent (0.08 g, 0.0055 mmol). Regardless of the catalyst delivery solvent used, the molar ratio of monomer/Pd785/DANFABA of the mixture was about 10000/1/5.6 in all mixtures.

Then, the compositions of Examples 1 to 6 prepared above were heated at 110° C. for 3 hours in a sealed glass bottle on a hot plate in an atmospheric environment. The resulting polymer was extracted in 5-10 g of THF by performing ultrasonic treatment for 1 hour. The THF extracts were analyzed by GPC using THF as the eluent to determine the _Mw of the extracted polymer. Extracted fractions were also analyzed by GC to determine the HexTD monomer content of the microreactions. GC analysis of unreacted monomer content was used to determine the ratio of HexTD monomer to polymer conversion (% conversion) during heating. Any insoluble material remaining in the glass bottle after THF extraction was dried in a vacuum oven at 110° C. for 20 hours to determine the residual fraction of THF-insoluble polymer (insoluble rate %) as an indication of the degree of curing.

The catalyst and cocatalyst delivery solvent used, the _Mw of the THF soluble fraction of the cured material, the insoluble material fraction, and the conversion of HexTD monomer to its polymer catalyzed by Pd785/DANFABA are shown in Table 1. From the data shown in Table 1, it can be seen that the use of polar solvents such as THF to deliver Pd785 catalyst or DANFABA co-catalyst will adversely affect the conversion rate of monomer to polymer and the M _w of the obtained polymer (Examples 1 and 2) . When EA was used in combination as cocatalyst delivery solvent to deliver Pd785 in non-polar solvents such as toluene (Example 5), CH (Example 3), MCH (Example 4), or TFT (Example 6), HexTD's The conversion and the resulting molecular weight will become higher.

Table 1 Example No. Delivery Pd785 Delivery of DANFABA _Mw ×1000 Intolerant rate % Conversion rates% 1 THF THF 42 <1 35 2 Toluene THF 201 45 45 3 CH EA 228 76 82 4 MCH EA 192 77 85 5 Toluene EA 263 76 88 6 TFT EA 268 94 93

Examples 7 to 13

A solution of Pd785 and DANFABA was prepared in general according to the procedures shown in Examples 1-6, except that the solvents were slightly changed as shown in Table 2, and then mixed with HexTD to form the compositions of Examples 7-13 thing. Then, in a sealed glass bottle on a hot plate, each composition was heated at 110° C. in an atmospheric environment. Record the time it takes for the liquid mixture to become a gel (gel time). The results are shown in Table 2. As can be seen from the results shown in Table 2, the data are consistent with the results shown in Examples 1 to 6. That is, the polymer conversion ratios shown in Table 1 agree with the polymerization ratios measured by gelation time. The gelation time in each of Examples 7 to 13 was affected by the catalyst or co-catalyst delivery solvent. The use of polar solvents such as THF to deliver Pd785 or DANFABA reduces the polymerization rate as shown by the increased gel time (Examples 7-9). The non-polar solvent increases the rate of polymerization as shown by the reduced gel time (Examples 10-13).

Table 2 Example No. Delivery Pd785 Delivery of DANFABA gel time 7 THF THF ＞180 minutes 8 Toluene THF ＞180 minutes 9 THF EA 6 minutes 10 MCH EA 3 minutes 11 Toluene EA 3 minutes 12 CH EA 2.5 minutes 13 TFT EA 2.5 minutes

Examples 14 to 17

(DSC measurement)

In a sealed glass vial, the catalyst and cocatalyst stock solutions were prepared under nitrogen as follows: Pd785 (0.015 g, 0.019 mmol) was dissolved in 1.6 g of TD (used in Examples 15 and 16), Pd785 (0.03 g , 0.038 mmol) was dissolved in 3.2 g of THF (used in Example 14), Pd785 (0.031 g, 0.039 mmol) was dissolved in 3.2 g of MCH (used in Example 17), DANFABA (0.174 g, 0.22 mmol) was dissolved In 3.2 g of THF (used in Examples 14 and 15), and DANFABA (0.174 g, 0.22 mmol) in 3.2 g of EA (used in Examples 16 and 17).

In a glass vial, a mixture of TD (1.92 g, 12 mmol) and BuNB (1.2 g, 7.98 mmol) was prepared and used for each of Examples 14-17. To this mixture was added a solution of Pd785 in the desired catalyst delivery solvent, as described above, and DANFABA in the desired cocatalyst delivery solvent, as described above. Regardless of the catalyst delivery solvent used, the molar ratio of monomer/Pd785/DANFABA of the mixture remained about 10500/1/5 in all compositions.

A small amount of the above mixture was used for DSC measurement in the range of 20°C to 150°C with a temperature gradient of 5°C/min. The exotherm generated during the polymerization was determined. About 1 g of each of these mixtures was heated at 110° C. for 3 hours in an aluminum pan, on a hot plate under atmospheric conditions. The weight of the material was measured before and after heating to determine the weight loss fraction. Likewise, each about 2 g of the residual mixture was heated at 110° C. in a sealed glass bottle. The time required for the liquid composition to become a gel (gel time) was recorded. The results are shown in Table 3.

The lowest exotherm (82 J/g) and a longer gel time (60 seconds) were observed when both the catalyst and cocatalyst were delivered in THF (Example 14). When delivering Pd785 in MCH and DANFABA in EA, a higher exotherm (237 J/g), shorter gel time (45 sec), and minimal Weight loss (20%), i.e. polar solvents such as THF provide lower polymerization efficiencies, while non-polar solvents such as MCH provide higher polymerization efficiencies. Figure 1 shows a DSC thermal image where solvent delivery using THF as a catalyst and co-catalyst increases the peak temperature, while delivery of Pd785 using MCH and DANFABA using EA reduces the peak temperature. The gelation time was the longest in Comparative Example 1 where no catalyst or co-catalyst was used to deliver the solvent. As evidenced by the late onset of the exotherm, the DSC thermal image of Figure 1 shows that, in Comparative Example 1, polymerization also begins at elevated temperatures of about 88°C. The results of Examples 14 to 17 and Comparative Example 1 confirm that the use of the catalyst to transport the solvent is not only beneficial to the better solubility or dispersibility of the catalyst and the co-catalyst in the monomer, but also to obtain the catalyst with a larger molecular weight. Polymers with better properties. In addition, as confirmed by the data shown in Table 3, non-polar solvents such as MCH are more favorable for polymerization efficiency than polar solvents such as THF.

table 3 Example No. Delivery Pd785 Delivery of DANFABA Weight loss (%) Gel time (seconds) Exothermic (J/g) Comparative Example 1 Solvent free Solvent free 49 540 272 Example 14 THF THF 37 60 82 Example 15 TD THF 55 45 134 Example 16 TD EA 29 50 138 Example 17 MCH EA 20 45 237

Examples 18 to 22

(DSC measurement)

The catalyst stock solutions of Pd785 prepared in Examples 14-17 were used in these Examples 18-21. Stock solutions of Pd785 prepared in TFT and LiFABA were used as cocatalysts in Example 22. Pd785 (0.032 g, 0.041 mmol) was dissolved in 3.2 g of TFT and LiFABA (0.174 g, 0.2 mmol) was dissolved in 3.2 g of THF.

A mixture of TD (1.92 g, 12 mmol) and BuNB (1.2 g, 7.98 mmol) prepared in a glass vial was used for each of Examples 18-22. To each composition was added a solution of Pd785 in the desired catalyst delivery solvent (0.16 g, 0.0019 mmol) and a solution of DANFABA (0.16 g, 0.01 mmol) in the desired cocatalyst delivery solvent. Irrespective of the catalyst delivery solvent used, the molar ratio of monomer/Pd785/DANFABA or LiFABA of the composition remained about 10500/1/5.3 in all examples.

A part of the above composition was used for DSC measurement in the range of 20°C to 250°C with a temperature gradient of 5°C/min. The exotherm generated during polymerization was determined. About 1 g of each of these compositions was heated at 110° C. for 3 hours in an aluminum pan on a hot plate in an atmospheric environment. The weight of the material was measured before and after heating to determine the weight loss fraction. Likewise, each about 2 g of the residual mixture was heated at 110° C. in a sealed glass bottle. Record the time it takes for the liquid mixture to become a gel (gel time). The results are shown in Table 4.

Table 4 Example No. Delivery Pd785 Delivery of LiFABA Weight loss (%) Gel time (seconds) Exothermic (J/g) Comparative Example 2 Solvent free Solvent free 100 >3 hours none Example 18 THF THF 33 1200 353 Example 19 TD THF -- -- 338 Example 20 THF EA 27 600 380 Example 21 MCH EA 33 270 369 Example 22 TFT EA 29 165 382

The polymerization efficiency determined by weight loss, gelation time, and exotherm produced by the Pd785/LiFABA system (Example 22) also followed the same behavior observed for Pd785/DANFABA shown in Examples 14-17, even though the effect was In this case it is less significant. However, the DSC thermograms shown in Figure 2 clearly show a shift to lower polymerization temperatures when Pd785 is delivered using a non-polar solvent such as MCH or TFT in combination with EA delivery of LiFABA. In Comparative Example 2, the weight loss was 100% after heating at 100°C for 3 hours and no gel was formed during the curing step, indicating that polymerization of the monomers did not occur under these conditions. This is further confirmed by the fact that no exotherm was observed during the DSC measurement for the composition of Comparative Example 2, indicating that no polymerization occurred. The results of Examples 18 to 22 and Comparative Example 2 confirm that the use of a suitable catalyst delivery solvent is not only conducive to better solubility or dispersibility of the catalyst and co-catalyst in the monomer, but also can obtain excellent film formation. Properties and other characteristic advantages of polymers.

Examples 23 to 28

According to the procedures shown in Examples 14-17, Pd785 and DANFABA stock solutions were prepared. Then, as shown in Table 5, except that NBANB (Examples 23 and 24), CyHexNB (Examples 25 and 26), and TD (Examples 27 and 28) were used as monomers and various solvents, generally Various compositions were prepared according to the procedures of Examples 14-17. In addition, in each of Examples 23 to 28, the molar ratio of the monomer/Pd785/DANFABA was maintained at about 10000/1/5. The compositions were cured in open aluminum pans at 110°C for 3 hours to generate weight loss data. The mixture was also cured at 110°C in a sealed glass vial to observe gel time. Table 5 shows the results obtained in Examples 23-28. Again, it was observed as either by weight loss (monomer loss) during a curing step of 3 hours at 110°C in an open aluminum pan or the time required to gel at 110°C in a sealed glass vial (solid polymer formation). ), the use of MCH to deliver Pd785 and EA to deliver DANFABA favors the polymerization efficiency compared to the use of THF to deliver Pd785 and DANFABA for polymerization.

table 5 Example No. monomer Delivery Pd785 Delivery of DANFABA Weight loss (%) Gel time (seconds) twenty three NBANB THF THF 25 120 twenty four NBANB MCH EA 20 80 25 CyHexNB THF THF twenty one 75 26 CyHexNB MCH EA 17 55 27 TD THF THF 36 60 28 TD MCH EA 26 45

Examples 29 to 37

Shelf Life Studies

As shown in Table 6 and Table 7, in each of Examples 29 to 37, the monomers used were TD and BuNB with a molar ratio of 60:40, and the catalyst and co-catalyst were transported with different solvents. Otherwise, various compositions were prepared substantially according to the procedures shown in Examples 14-22. The compositions prepared in glass bottles were kept at ambient temperature and the viscosities were observed visually. Record the viscosity increase as non-stick, slightly sticky, sticky, glue, soft film and film to estimate the viscosity at ambient temperature or the degree of heat curing. Good pot life is considered good if the mixture remains non-sticky, slightly tacky, or tacky, and the mixture is still capable of being cast on a substrate, cured and formed into a film. The results are shown in Table 6 (LiFABA as a cocatalyst) and Table 7 (DANFABA as a cocatalyst). Compositions containing LiFABA as a cocatalyst (Examples 29-33) generally had better pot life than DANFABA (Examples 34-37). This observation is consistent with the DSC thermograms shown in Figure 2 (LiFABA) and Figure 1 (DANFABA), where the composition containing LiFABA as a cocatalyst started to solidify (exothermic) at about 70°C (Figure 2), In contrast, the composition containing DANFABA as a cocatalyst started to solidify (exothermic) at about 30°C (Figure 1). The choice of catalyst and co-catalyst delivery solvent also affects the service life. Using THF to deliver the catalyst and co-catalyst will prolong the service life, but using TFT or MCH will shorten the service life.

Table 6 Example No. Delivery Pd785 Delivery of LiFABA viscosity 3 hours Day 1 Day 2 Day 3 Day 4 Day 7 29 THF THF Not sticky Not sticky Not sticky Not sticky Not sticky Not sticky 30 THF EA Not sticky Not sticky Not sticky Not sticky Not sticky Not sticky 31 MCH EA Not sticky Not sticky Not sticky Not sticky Not sticky Not sticky 32 TFT THF Not sticky Not sticky Not sticky Not sticky Not sticky Not sticky 33 TFT EA Not sticky Not sticky slightly sticky slightly sticky slightly sticky slightly sticky

Table 7 Example No. Delivery Pd785 Delivery of DANFABA viscosity 0.75 hours 1 hour 1.5 hours 2 hours 3 hours 4 hours 7 hours 1 day 34 THF THF Not sticky Not sticky Not sticky Not sticky sticky very sticky glue glue 35 TD THF Not sticky sticky glue glue glue glue glue Soft film 36 TD EA Not sticky Not sticky Not sticky slightly sticky glue glue glue glue 37 MCH EA sticky very sticky glue glue Soft film Soft film Soft film membrane

Example 38

Stock solutions of Pd785 (1 wt.%) and LiFABA (5 wt.%) were prepared in THF as solvent. Then, PENB (5.95 g, 30 mmol) was mixed with Pd785 solution (0.24 g, 0.003 mmol) and LiFABA solution (0.15 g, 0.009 mmol). The molar ratio of monomer:Pd785:LiFABA was about 10000:1:3. The composition was knife-coated on a glass substrate and cured in an oven at 80° C., 110° C., 120° C., and 130° C. for 1 hour to form a film having a thickness of about 100 to 300 μm. TGA was used to determine the temperature (T _d5 ) at which a 5 wt.% film was lost under a nitrogen environment with a temperature gradient of 10°C/min. This measurement indicated that any residual monomer was still present in the film due to insufficient cure or less than 100% monomer conversion to polymer. The dielectric constant (Dk) and dielectric loss factor (tanδ or Df) of various films were measured at a frequency of 10 GHz. Furthermore, about 0.1-0.2 g of the films formed at various curing temperatures were extracted with THF (6-8 g) at 30° C. for 60 minutes to remove unreacted monomers present in the films. The THF extract was analyzed by GC to determine the residual monomer content in the membrane and to calculate the conversion of PENB monomer to polymer membrane. The data shown in Table 8 indicate that there is a correlation between conversion (the amount of residual monomer present in the film), T _d5 as determined by TGA, and dielectric loss factor (Df). Figure 3 shows the relationship between residual monomer and Df. Conversion is calculated from the amount of residual monomer remaining in the membrane. From the data shown in Table 8, it can be seen that the more residual monomer, the lower the T _d5 . In addition, with the increase of residual monomer, Df will become higher.

This Example 38 further demonstrates the importance of employing suitable bulk polymerization conditions whereby maximum conversion of monomers can be achieved for improved thermal and dielectric properties.

Table 8 Curing temperature (°C) Residual monomer (%) Monomer conversion rate (%) T _d5 (°C) Df (10GHz) 80 12.5 87.5 138 0.00309 110 8.5 91.5 203 0.00254 120 5.1 94.9 227 0.00215 130 2 98 232 0.00186

Example 39

Pd785 (1 wt.%) in THF or MCH and DANFABA (5 wt.%) in THF or EA were prepared in sealed vials. Two compositions were prepared by adding Pd785/THF and DANFABA/THF to HexNB (3.56 g, 21.2 mmol) or Pd785/MCH and DANFABA/EA to HexNB (3.56 g, 21.2 mmol). The monomer:Pd785:DANFABA ratio was maintained at about 10000:1:5. These compositions were knife-coated on glass substrates and cured at 80°C, 100°C, and 120°C for 1 hour, respectively. The dielectric dissipation factor (Df) was measured at 10 GHz. Figure 4 shows that the Df values are as low as expected when Pd785 is delivered in MCH and DANFABA is delivered in EA compared to when both the catalyst and cocatalyst are delivered in THF.

Examples 40 to 45

Following the procedures shown in Examples 14-17, using MCH as solvent in Pd785 and EA as solvent in DANFABA, stock solutions of Pd785 and DANFABA were prepared. Then, the following compositions were prepared: CyHexNB/BuNB (60/40 mol ratio) in Example 40, TD/BuNB (60/40 mol ratio) in Example 41, CyHexNB/BuNB/ NBD (50/40/10 mol), TD/BuNB/NBD in Example 43 (50/40/10 mol), CyHexNB/BuNB/CPD3 in Example 44 (50/40/10 mol) ear ratio), CyHexNB/BuNB/CPD3 in Example 45 (50/40/10 molar ratio) and 4 parts thermal radical initiator per hundred parts DCP. In each composition, the molar ratio of monomer/Pd785/DANFABA remained about 10000/1/5. The compositions were cast on a glass substrate and knife-coated to form a rectangular shape of about 10 cm x 6 cm, and then cured at 110° C. for 3 hours to form a rectangular film with a thickness of about 200 to 500 μm. The films were further vacuumed at about 120-150°C for 3-6 hours to remove any residual monomer present. The rectangular film was cut into small rectangles for TMA, and electrical properties such as dielectric constant (Dk) and dielectric loss factor (Df) at a frequency of 10 GHz were measured. In Table 9 are shown glass transition temperature (T _g ), thermal decomposition temperature as the temperature at which 5 wt. % of film weight is lost (T _d5 ), coefficient of thermal expansion (CTE), the thermal decomposition temperature of films prepared by the process described in the present invention Dk and Df.

Table 9 Example No. CTE (ppm/K) T _g (ᵒC) T _d5 (ᵒC) Dk at 10GHz Df at 10GHz Comparative Example 3 109 313 331 2.4 0.00820 Example 40 99 350 328 2.21 0.0010 Example 41 91 329 312 2.27 0.0009 Example 42 88 329 294 2.36 0.0008 Example 43 86 317 301 2.23 0.0010 Example 44 86 329 284 2.21 0.0022 Example 45 89 364 288 2.20 0.0010

The films can have high _Tg , high _Td5 , low CTE, low Dk, and low Df. Further, as in Example 45, by adding a thermal radical generator such as DCP, the Df at 10 GHz is higher when the second curing route of removing residual monomer is used than the embodiment without the second curing route of removing residual monomer. 44 further decreased to 0.001.

Example 46

Pd785 (1 wt.% in THF or MCH), Rhodorsil-2074 (about 5.5 wt.% in THF, EA or BuNB) and UV-CATA (about 7 wt.%) were mixed with BuNB (3 g, 20 mmol) to prepare A series of compositions. The molar ratio of BuNB to Pd785 was set to 10000:1 (0.002 mmol of Pd785) and the molar ratio of BuNB to Rhordorsil-2074 or UV-CATA was set to 10000:4 (0.008 mmol of Rhordorsil-2274 or UV-CATA) ). These compositions (1 g each) were cured at 110°C for 2 hours on an aluminum pan on a hot plate (open to the atmosphere). The final weight of the formed film was determined and the amount of monomer lost during curing was calculated. Weight loss or monomer loss is indicative of the efficiency of the curing step when using different solvents to deliver the catalyst and cocatalyst. Table 10 shows the weight loss data. This data confirms that the reactivity of the catalyst and cocatalyst is low when transporting catalyst and co-catalyst in a coordinating solvent such as THF, while the curing efficiency is improved when Pd785 is transported in a non-coordinating solvent such as MCH.

The compositions were also evaluated for shelf life stability at ambient temperature. The slow polymerization of these compositions causes them to slowly become sticky materials that eventually become glues or films. If the composition can be cast with increased viscosity, it can be used to form a film. However, once the composition becomes a glue or film, these are no longer usable. Solutions that are considered non-sticky (n. sticky), slightly sticky (s. sticky), and very sticky (v. sticky) can be poured. Table 11 shows the pot life of the compositions of Example 46, demonstrating that the pot life can be altered by the delivery of the solvent through a catalyst or co-catalyst. When UV-CATA is used as a cocatalyst, it has better shelf life stability than Rhordorsil-2074. MCH delivering Pd785 and EA delivering UV-CATA had the best lifetime stability (2 weeks), best curing efficiency and lowest weight loss during curing (31% wt. loss, 69% monomer conversion to film) ).

Table 10 Delivery Pd785 Delivery Rhordorsil-2074 Conveying UV-CATA Film weight after curing (g) Weight loss (%) THF THF 0.20 80 MCH THF 0.44 56 MCH EA 0.40 60 THF THF 0.40 60 MCH THF 0.48 52 MCH EA 0.69 31 MCH BuNB 0.47 53

Table 11 Delivery Pd785 Delivery Rhordorsil-2074 Conveying UV-CATA Day 0 Day 8 Day 12 Day 14 Day 23 THF THF Not sticky Not sticky slightly sticky very sticky glue MCH THF Not sticky Not sticky slightly sticky glue gel MCH EA Not sticky Not sticky slightly sticky glue gel THF THF Not sticky Not sticky Not sticky Not sticky Not sticky MCH THF Not sticky Not sticky Not sticky slightly sticky sticky MCH EA Not sticky Not sticky Not sticky sticky glue MCH BuNB Not sticky slightly sticky gel gel gel

Example 47

A series of compositions were prepared by mixing Pd520 (0.9 wt.% in THF, EA or BuNB) and Rhordorsil-2074 (about 5.5 wt.% in THF or EA) with BuNB (3 g, 20 mmol). The molar ratio of BuNB to Pd520 was maintained at 10000:1 (0.001 mmol of Pd520) and the molar ratio of BuNB to Rhordorsil-2074 was maintained at 10000:4 (0.016 mmol of Rhordorsil-2074). 1 g of each of these compositions was placed on an aluminum pan and exposed to 3 J/cm ² radiation at a wavelength of 365 nm. All compositions turned into sticky films or gels upon irradiation, indicating that they have photocurable capabilities.

The shelf life stability of the photocurable compositions was also evaluated at ambient temperature, under yellow light to prevent any optical reaction. The slow thermal polymerization of these mixtures makes them sticky and eventually a glue or film. If the composition can be cast with increased viscosity, it can be used to form a film. However, once the formulation becomes gel-like or film-like, these are no longer usable. Solutions that are considered non-viscous (n.viscous), slightly viscous (s.viscous), and very viscous (v.viscous) can be poured. Table 12 shows the shelf life of the compositions of Example 47, demonstrating that the shelf life can be changed by the catalyst or co-catalyst delivery solvent of the photocurable compositions. Using a complexing solvent such as THF to deliver Rhodorsil-2074 can improve the lifetime stability of these photocurable compositions.

Table 12 Delivery Pd-520 Delivery Rhordorsil-2074 Day 0 Day 9 Day 13 Day 16 Day 26 BuNB THF Not sticky slightly sticky slightly sticky sticky sticky THF THF Not sticky sticky sticky very sticky very sticky BuNB EA Not sticky glue gel gel gel EA EA Not sticky glue glue gel gel

Example 48

A mixture of Pd785 (0.039 g, 0.005 mmol) and LiFABA (0.13 g, 0.015 mmol) was mixed with THF (4.97 g) and 0.1 g of this mixture was added to HexNB (8.92 g, 53.1 mmol). The molar ratio of HexNB to Pd785 was set to 52100:1 (0.001 mmol of Pd785) and the molar ratio of HexNB to LiFABA was set to 52100:3 (0.003 mmol of LiFABA). The solution was sonicated for 90 minutes at ambient temperature and filtered through a 0.2 µm PTFE filter. The solution was knife-coated on a glass substrate and cured at 110°C for 3 hours under nitrogen to obtain a 140-µm-thick film. The UV-VIS spectrum of the suspended film was measured and shown in FIG. 5 . The transparency (%T) obtained in the 400-800 nm wavelength region is greater than 90%, which is close to the maximum expected %T of 92%. Therefore, the films formed by the method described in the present invention are suitable for optical applications requiring films with high transparency.

Examples 49 to 52

Pd785 (0.03 g) was dissolved in dry THF (3.2 g) to prepare a 1 wt.% solution. In a glass vial, a portion of this solution (1.01 g) was mixed with distilled water (0.083 g) to form a Pd785/water/THF mixture, where the water content of the mixture was about 7.6 wt.%, and the glass vial was capped with a septum ( septum cap) seal. In a glass vial sealed with a septum cap, LiFABA (0.174 g) was dissolved in anhydrous THF (3.2 g) or anhydrous EA (3.2 g) to form an approximately 5 wt.% LiFABA solution. TD (1.92 g, 12 mmol) and BuNB (1.2 g, 8 mmol) were mixed in a glass bottle (TD/BuNB 60/40 molar ratio). A solution of LiFABA (0.16 g) and Pd785 (0.16 g) was added to the monomer mixture. Regardless of the catalyst delivery solvent used, the molar ratio of monomer/Pd785/LiFABA of the composition was maintained at about 10000/1/5 in all examples. Aqueous Pd785 solutions were used fresh within 1 hour of preparation or used after aging for 16 days to allow for any Pd785 conversion caused by reaction with water present in the medium. A small sample of the mixture (approximately 0.8 g to 1 g) was heated in a glass bottle at 110°C and the time required for the liquid mixture to become solid (gel time) was recorded for each mixture. The compositions of Examples 49 to 52 are shown in Table 13, including Examples 18 and 20 without any water added to the Pd785/THF solution. The gelation time clearly shows that the polymerization efficiency increases when water is present in the Pd785/THF catalyst delivery medium. The polymerization efficiency was further improved upon aging of the Pd785/THF/water mixture. Figure 6 shows a comparison of the DSC charts of Example 18 and Example 49, which clearly demonstrate that the polymerization efficiency is improved by setting the exotherm onset temperature lower if water is contained in the Pd785/THF catalyst delivery medium.

Table 13 Example No. Pd785 conveying medium LiFABA delivery medium gel time exothermic Example 18 THF THF 1200 seconds 353J/g Example 49 THF/water (fresh) THF 360 seconds 324J/g Example 50 THF/Water (aging) THF 180 seconds -- Example 20 THF EA 600 seconds -- Example 51 THF/water (fresh) EA 240 seconds -- Example 52 THF/Water (aging) EA 150 seconds --

Examples 53 to 57

Shelf Life Studies

Pd785 was dissolved in various solvents (dichloromethane, toluene, xylene or THF) to form a 1 wt.% solution. A portion (3 g) of the Pd785/THF solution was mixed with distilled water (0.3 g with 10 wt.% water in the catalyst system) and aged at ambient temperature for 15 days. LiFABA was dissolved in anhydrous EA to form a 5 wt.% solution. HexNB (3.56 g, 20 mmol) was mixed with Pd785 solution (0.16 g) and LiFABA solution (0.1 g). The molar ratio of monomer/Pd785/LiFABA of each composition was maintained at about 10000/1/3. The mixtures were maintained at an ambient temperature of about 23°C and the viscosity of the compositions was visually recorded as non-stick (n. sticky), slightly sticky (s. sticky), sticky (v) or glue to evaluate the composition Shelf life. All compositions were non-sticky shortly after preparation and remained that way for at least 1 day (24 hours) before viscosity increased. Tables 15 and 16 show these observations. Good shelf life is considered good if these mixtures can be cast on substrates such as glass to form films (ie, not gelled). The shelf life of the composition depends on the Pd785 catalyst transporting solvent, and is regulated by the coordination ability of the catalyst transporting solvent. The coordination ability of the catalyst transporting solvent is recorded as the coordination of the amount of the coordination ability of the solvent to the transition metal. Capability index (α) (refer to Chem. Eur. J. 2020, 26, 4350-4377). Solvents with higher coordination ability for transition metals such as THF (α=-0.3) have longer shelf life, while solvents with lower coordination ability for transition metals such as toluene (α=-1.3) have Shorter shelf life. Although capable of coordinating transition metals due to the presence of lone pairs of electrons in chlorine (J.Am.Chem.Soc. 1989, 111, 3762-3764), methylene chloride is generally considered to be polar with an alpha value of 1.8. Non-coordinating solvent (see J.Am.Chem.Soc. 1998, 110, 5293). The shelf life results shown in Table 14 indicate that dichloromethane acts as a non-coordinating solvent. Therefore, the shelf life of the composition of the present invention can be adjusted by selecting an appropriate Pd785 catalyst delivery solvent. The exception was the composition comprising Pd785/THF/water, as described above, suggesting that the presence of water during aging would allow such catalyst systems to be converted to more active species.

About 1 g each of the compositions of Examples 53, 56 and 57 in sealed glass vials were heated on a hot plate to 120°C and the time for the mixture to gel was recorded. The composition of Example 53 became a gel within 3 minutes and 30 seconds. As shown in Table 14, the composition of Example 56 gelled within 5 minutes, and the composition of Example 57 gelled within 3 minutes and 15 seconds, which confirms that the addition of water in the catalyst delivery medium increases the polymerization efficiency while reducing the Shelf life. The reactivity of the composition of Example 57 was similar to that of the composition of Example 53 but not to that of Example 56, although more coordinated THF was used in both the catalyst delivery media of Examples 56 and 57 the reactivity of the composition. In Example 57, the catalyst transport medium cannot be decoordinated by the presence of water in the catalyst transport medium. This is due to the presence of lone pairs of electrons in oxygen, so water has a high coordination ability for transition metals. The alpha value of water is set to zero in the coordination ability scale, which makes it easier to coordinate with transition metals than THF. These differences in catalytic activity must occur due to the reaction of water with Pd785 to generate more active catalyst species in situ. The catalytic activity of Pd785/THF/water (in Example 57, the gel time was 3 minutes and 15 seconds at 120°C) was similar to that of Pd785/CH ₂ Cl ₂ (in Example 53, the gel time was 3 minutes and 30 seconds) , but the shelf life of Example 57 was longer (at least 2 times longer) than that of Example 53 (refer to FIG. 15 ).

Table 14 Example No. solvent alpha level Day 0 Week 3 Week 4 Week 7 Example 55 Xylene -0.5 Not sticky Not sticky slightly sticky sticky Example 56 THF -0.3 Not sticky Not sticky Not sticky Not sticky

Table 15 Example No. solvent alpha level Day 2 Day 3 Day 4 Day 7 Example 53 CH ₂ Cl ₂ -1.8 sticky gel Example 54 Toluene -1.3 Not sticky Not sticky slightly sticky sticky Example 57 THF/water 0～-0.3 Not sticky slightly sticky sticky

Example 58

The compositions of Examples 53, 55, 56, and 57 were coated on a glass substrate by knife coating to form a rectangular film of about 100-160 μm, and cured at 130° C. for 2 hours in a nitrogen environment. The film thickness of Example 53 was 115 μm; the film thickness of Example 55 was 110 μm; the film thickness of Example 56 was 160 μm; and the film thickness of Example 57 was 150 μm. Glass transition temperature (T _g ) and coefficient of thermal expansion (CTE) were determined by thermomechanical analysis (TMA), 5 wt.% decomposition temperature (T _d5 ) was determined by thermogravimetric analysis (TGA), and tensile strength was determined by Instron Strength, Young's Modulus and Elongation at Break (ETB). The dielectric constant (Dk) and dielectric dissipation factor (Df) were also measured at a frequency of 10 GHz. Table 16 shows the results obtained. The results obtained show that when sufficiently high polymerization temperatures and longer reaction times are utilized, the films formed using the compositions can be used to adjust their polymerization efficiency and shelf life by adjusting their polymerization efficiency and shelf life (i.e., by changing the catalyst delivery solvent to change the contact ratio. medium reactivity) becomes a film with improved thermomechanical properties, low dielectric constant and low dielectric dissipation factor. These examples demonstrate the benefits obtained by practicing the present invention. It is important to note that adjustments to the catalyst reactivity and shelf life of the compositions of the invention described in this specification do not affect the thermal, mechanical or electrical properties of the polymer films formed therefrom.

Table 16 Example No. Dk Df CTE (ppm/K) T _g (°C) T _d5 (°C) Tensile strength (MPa) Young's modulus (GPa) ETB (%) Example 53 2.28 0.00037 182 248 373 17 0.34 82 Example 55 2.21 0.00040 176 242 376 -- -- -- Example 56 2.30 0.00038 182 240 372 16 0.39 86 Example 57 2.26 0.00027 207 235 374 twenty three 0.53 88

Comparative Example 1

A mixture of TD (3.85 g, 24.0 mmol) and BuNB (2.4 g, 16 mmol) was prepared in a glass vial and used for polymerization. To this mixture was added Pd785 (0.0031 g, 0.0039 mmol) and DANFABA (0.016 g, 0.02 mmol). The molar ratio of monomer/Pd785/DANFABA of the mixture is about 10250/1/5.1, which is similar to the catalyst usage used in Examples 14-17. Some powders that settled on the bottom of the bottle indicated that the catalyst and co-catalyst could not be completely dissolved in the absence of the catalyst delivery solvent. A sample of this composition was analyzed by DSC. About 1 g of this mixture was heated at 110° C. for 3 hours in an aluminum pan on a hot plate under atmospheric conditions. The weight of the material was measured before and after curing to determine the weight loss fraction. Likewise, about 2 g of the mixture was heated at 110°C in a sealed glass bottle. The time for the liquid mixture to become a gel (gel time) was recorded. The results are shown in Table 3.

Comparative Example 2

A mixture of TD (3.85 g, 24 mmol) and BuNB (2.4 g, 16 mmol) was prepared in a glass vial and used for polymerization. To this mixture was added Pd785 (0.0031 g, 0.0039 mmol) and LiFABA (0.017 g, 0.02 mmol). The molar ratio of monomer/Pd785/LiFABA of the mixture is about 10250/1/5.1, which is similar to the catalyst usage used in Examples 18-22. Some powders that settled on the bottom of the bottle indicated that the catalyst and co-catalyst could not be completely dissolved in the absence of the catalyst delivery solvent. A sample of this composition was analyzed by DSC. About 1 g of this mixture was heated at 110° C. for 3 hours in an aluminum pan on a hot plate under atmospheric conditions. The weight of the material was measured before and after curing to determine the weight loss fraction. Likewise, about 2 g of the mixture was heated at 110°C in a sealed glass bottle. The time for the liquid mixture to become a gel (gel time) was recorded. The results are shown in Table 4.

Comparative Example 3

Pd785 (0.031 g, 0.039 mmol) was dissolved in about 3.2 g of TESNB as the catalyst delivery medium. DANFABA (0.174 g, 0.22 mmol) was dissolved in 3.2 g of TESNB as a cocatalyst delivery medium. TD (1.6 g, 9.98 mmol), BuNB (1.2 g, 7.98 mmol) and TESNB (0.24 g, 1.11 mmol) were mixed in a glass bottle, and Pd785 in TESNB (0.16 g) and TESNB (0.14 g) were added DANFABA. The total amount of TESNB present in the mixture was 0.54 g (1.99 mmol). The molar ratio of the TD/BuNB/TESNB mixture was 50/40/10. About 1 g of this mixture was heated at 110° C. for 3 hours in an aluminum pan on a hot plate under atmospheric conditions. The weight of the material was measured before and after curing to determine the weight loss fraction of 18%. Likewise, about 2 g of the mixture was heated at 110°C in a sealed glass bottle. The time for the liquid mixture to become a gel (gel time) was recorded as 150 seconds. This Comparative Example 3 shows that a polar monomer such as TESNB can be used as a catalyst transport medium instead of a catalyst transport solvent. The properties of TD/BUNB/TESNB (50/40/10) films using MCH to deliver Pd785 and EA to deliver DANFABA were determined and are shown in Table 9. Although the addition of polar monomers such as TESNB, which can replace MCH and EA, does not adversely affect the glass transition temperature and CTE, the dielectric loss factor (Df) of this composition is significantly higher (0.0082). This suggests that polar monomers capable of dissolving catalyst or co-catalyst components are not necessarily beneficial for other properties such as dielectric loss factors.

While the invention has been illustrated by some of the foregoing embodiments, it should not be construed as limited thereto, but rather should be understood to include the general field as disclosed above without departing from the spirit and scope of the invention, Various modifications and implementations are possible.

none

Hereinafter, embodiments according to the present invention will be described with reference to the following drawings and/or images. When a drawing is provided, the drawing is a simplified portion of various embodiments of the invention and is for illustration purposes only.

Fig. 1 shows a differential scanning calorimetry (DSC) thermogram obtained by using one type of catalyst activator described in this specification in each embodiment of the present invention.

[ Fig. 2] Fig. 2 shows a differential scanning calorimetry (DSC) thermogram obtained by using another type of catalyst activator described in this specification in each embodiment of the present invention.

FIG. 3 is a graph showing the correlation between the dielectric loss factor (Df) and the residual % of monomers present in films formed from various compositions according to the embodiment of the present invention.

Fig. 4 is a bar graph showing the dielectric loss factor (Df) at various curing temperatures for films formed from various compositions according to the embodiments of the present invention, comparing the transfer into methylcyclohexane (MCH) Catalysts (eg Pd785), activators or cocatalysts (eg DANFABA) delivered into ethyl acetate (EA), and catalysts and cocatalysts delivered into tetrahydrofuran (THF).

[ Fig. 5] Fig. 5 shows an ultraviolet-visible (UV-VIS) spectrum of a free-standing film formed from the composition of the embodiment of the present invention.

Fig. 6 shows a differential scanning calorimetry (DSC) thermogram comparing one embodiment of the present invention in which the catalyst described in this specification contains a small amount of water and another embodiment in which the catalyst does not contain water.

Claims (20)

A film-forming composition comprising: a) one or more olefin monomers of general formula (I):

(I) where m is an integer of 0, 1 or 2;

is a single bond or a double bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, straight-chain or branched (C ₃ -C ₁₆ ) alkyl, perfluoro(C ₁ -C ₁₂ ) alkyl, (C ₃ -C ₁₂ ) cycloalkyl, (C ₆ -C ₁₂ ) bicycloalkyl, (C ₇ -C ₁₄ ) tricycloalkyl, (C ₆ -C ₁₀ )aryl, (C ₆ -C ₁₀ )aryl(C ₁ -C ₆ )alkyl, perfluoro(C ₆ -C ₁₀ )aryl, perfluoro(C ₆ -C ₁₀ ) Aryl (C ₁ -C ₆ ) alkyl, methoxy, ethoxy, straight or branched (C ₃ -C ₁₆ ) alkoxy, epoxy (C ₁ -C ₁₀ ) alkyl, epoxy (C ₁ -C ₁₀ )alkoxy(C ₁ -C ₁₀ )alkyl, epoxy(C ₃ -C ₁₀ )cycloalkyl, perfluoro(C ₁ -C ₁₂ )alkoxy, (C ₃ - C ₁₂ ) cycloalkoxy, (C ₆ -C ₁₂ ) bicycloalkoxy, (C ₇ -C ₁₄ ) tricycloalkoxy, (C ₆ -C ₁₀ ) aryloxy, (C ₆ -C ₁₀ ) ) aryl (C ₁ -C ₆ ) alkoxy group, perfluoro (C ₆ -C ₁₀ ) aryloxy group and perfluoro (C ₆ -C ₁₀ ) aryl (C ₁ -C ₃ ) alkoxy group group; or one of R ₁ and R ₂ and one of R ₃ and R ₄ together with the carbon atoms to which they are bonded form a substituted or unsubstituted (C ₅ -C ₁₄ ) which may have more than one double bond ) ring, (C ₅ -C ₁₄ )bicyclic or (C ₅ -C ₁₄ )tricyclic; b) an organopalladium compound selected from the group comprising: bis(triphenylphosphine)palladium(II) chloride ; Bis(triphenylphosphine)palladium(II) dibromide; Bis(triphenylphosphine)palladium(II) diacetate; Bis(triphenylphosphine)bis(trifluoroacetic acid)palladium(II); Bis(tricyclohexyl) phosphine) palladium(II) dichloride; bis(tricyclohexylphosphine) palladium(II) dibromide; bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785); bis(tricyclohexylphosphine)bis (trifluoroacetic acid)palladium(II); bis(tris-p-tolylphosphine)palladium(II) dichloride; bis(tris-p-tolylphosphine)palladium(II) dibromide; bis(tris-p-tolylphosphine) Palladium(II) diacetate; bis(tri-p-tolylphosphine)bis(trifluoroacetic acid)palladium(II); palladium(II) ethylhexanoate; palladium(II) dichlorobis(benzonitrile); platinum chloride (II); platinum(II) bromide; and bis(triphenylphosphine)platinum dichloride; c) an activator selected from the group consisting of: lithium tetrafluoroborate; lithium trifluoromethanesulfonate; four (Pentafluorophenyl) lithium borate; Tetrakis (pentafluorophenyl) borate lithium ether complex (LiFABA); Tetrakis (pentafluorophenyl) borate sodium ether complex (NaFABA); Tetrakis (pentafluorophenyl) borate trityl ether complex (tritylFABA); tetrakis (pentafluorophenyl) borate trityl ether complex (tropyliumFABA); tetrakis (pentafluorophenyl) borate lithium isopropoxide compound; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexafluorophosphate; Lithium hexafluorophenyl phosphate; Lithium hexafluoroarsenate; Lithium phenylarsenate; Lithium hexa(pentafluorophenyl)arsenate; Lithium hexa(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexa(pentafluorophenyl) antimonate; Lithium hexa(3,5-bis(trifluoromethyl) phenyl) antimonate; Lithium tetrakis(pentafluorophenyl) aluminate; Tris(nonafluorobiphenyl) fluoride Lithium aluminate; lithium (octyloxy)tris(pentafluorophenyl)aluminate; lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; methyltris(pentafluorophenyl)aluminum and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); and d) a solvent selected from the group consisting of water, ortho-xylene, para-xylene, meta-xylene, benzene, fluorobenzene , 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1,2,3 ,4-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, toluene, ethylbenzene, trifluorotoluene, pentafluoroethylbenzene, chlorobenzene, nitrobenzene, 1,4 -Diethane, dimethylacetamide, dimethylformamide, diethylformamide, furan, tetrahydrofuran, diethyl ether, dimethoxyethane, ethyl acetate, propyl acetate, butyl acetate , Amyl acetate, acetone, methyl ethyl ketone, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, ethylcyclopentane, ethylcyclohexane, dibromoethane, Mixtures of dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and any combination of these. The film-forming composition according to claim 1, wherein m is 0 or 1;

is a single bond or a double bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are independently selected from the group consisting of hydrogen, straight or branched chain (C ₄ -C ₁₆ ) alkyl, (C ₃ - C ₁₀ ) cycloalkyl, (C ₃ -C ₁₀ ) cycloalkenyl, (C ₆ -C ₁₂ ) bicycloalkyl, (C ₆ -C ₁₂ ) aryl and (C ₆ -C ₁₂ ) aryl (C 6 -C 12 ) aryl groups ₁ -C ₆ ) group of alkyl groups; or one of R ₁ and R ₂ and one of R ₃ and R ₄ together with the carbon atoms to which they are bound form, substituted or unsubstituted, may have more than one (C ₅ -C ₁₄ ) ring, (C ₅ -C ₁₄ ) bicyclic or (C ₅ -C ₁₄ ) tricyclic ring of a double bond. The film-forming composition according to claim 1, further comprising a compound selected from the group consisting of: a compound of the general formula (A1):

(A1) wherein, b is an integer from 2 to 6; Z is a bond or R ₉ R ₁₀ SiOSiR ₁₁ R ₁₂ , wherein each of R ₉ , R ₁₀ , R ₁₁ and R ₁₂ is the same or different, and is independently selected from the group consisting of the group of methyl, ethyl and straight or branched (C3 _{- C6} )alkyl _{; R5} , R6, _R7 and _R8 are the same or different, and are each independently selected from the group consisting of hydrogen, methyl , ethyl and linear or branched (C ₃ -C ₁₆ ) alkyl groups; and compounds of general formula (A2):

(A2) wherein, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different, and are each independently selected from the group consisting of hydrogen, methyl, ethyl and straight or branched (C ₃ -C ₁₆ ) alkyl groups group; and compounds of general formula (A3):

(A3) wherein, L is a bond or a divalent linking group or a spacer group, which is selected from the group consisting of: methylene, ethylidene, straight-chain or branched (C ₃ -C ₁₆ ) alkylene, (C ₃ -C ) ₁₆ ) Cycloalkylene, (C ₅ -C ₈ ) heterocycle, (C ₆ -C ₁₂ ) arylene, (C ₅ -C ₁₂ ) heteroarylene and -(CH ₂ ) _c O(CH ₂ ) _c -, wherein c is an integer from 1 to 6, and each CH ₂ may be substituted by methyl, ethyl, straight or branched (C ₃ -C ₁₆ ) alkyl and (C ₆ -C ₁₂ ) aryl groups, wherein the hydrogen moiety in methylene, ethylidene or (C ₃ -C ₁₆ )alkylene may be selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched perfluoro(C ₃ -C ₁₆ ) group substitution of alkyl groups; R ₁₇ and R ₁₈ are the same or different, and are each independently selected from methyl, ethyl, linear or branched (C ₃ -C ₁₂ ) alkyl , (C ₆ -C ₁₂ ) aryl and (C ₆ -C ₁₂ ) aryl(C ₁ -C ₁₂ ) alkyl groups, wherein the hydrogen moiety in methyl, ethyl or (C ₃ -C ₁₂ ) alkyl groups may be substituted by a group selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched (C ₃ -C ₁₂ ) perfluoroalkyl; Ar ₁ and Ar ₂ are the same or different , and are independently selected from (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₂ ) aryl (C ₆ -C ₁₂ ) aryl (C ₁ -C ₄ ) alkyl and (C ₆ -C ₁₂ ) aryl (C ₁ -C ₄ ) alkoxy groups substituted (C ₆ ) -C ₁₂ ) arylene or (C ₆ -C ₁₂ )heteroarylene. The film-forming composition of claim 1, wherein the monomer of general formula (I) is selected from the group comprising:

Bicyclo[2.2.1]hept-2-ene (norbornene or NB);

Bicyclo[2.2.1]hept-2,5-diene (norbornadiene or NBD);

5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);

5-Decylbicyclo[2.2.1]hept-2-ene (DecNB);

5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

5-ethylenebicyclo[2.2.1]hept-2-ene (ENB);

5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB);

5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);

5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB);

5-phenylbicyclo[2.2.1]hept-2-ene (PhNB);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

2,2'-bis(bicyclo[2.2.1]heptane-5-ene) (NBANB);

1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD);

2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD);

1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene (TDD);

3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD); and

3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3). The film-forming composition according to claim 3, wherein the compound of the aforementioned general formula (A1) is selected from the group comprising:

1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB); and

1,4-Bis(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBC4NB). The film-forming composition according to claim 3, wherein the compound of the general formula (A2) is

1,4,4a,4b,5,8,8a,8b-Octahydro-1,4:5,8-Dimethylbiphenyl ((NBD)2). The film-forming composition according to claim 3, wherein the compound of the aforementioned general formula (A3) is selected from the group comprising:

3,3'-((oxobis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazacyclopropene);

4,4''-bis(3-(trifluoromethyl)-3H-diazacyclopropen-3-yl)-1,1':3',1''-bitriphenyl;

3,5-bis(4-(3-(trifluoromethyl)-3H-diazacyclopropen-3-yl)phenyl)pyridine; and

3,3'-((Perfluoropropane-2,2-diyl)bis([1,1'-biphenyl]-4',4-diyl))bis(3-(trifluoromethyl) -3H-diazacyclopropene). The film-forming composition according to claim 1, further comprising an inorganic filler. The film-forming composition according to claim 1, further comprising an organic filler. The film-forming composition as claimed in claim 1, which is selected from the group comprising the following: 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 1,4,4a,5,8,8a-hexa Hydrogen-1,4:5,8-dimethylnaphthalene (TDD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA) ; 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB), 1,4,4a,5,8,8a- Hexahydro-1,4:5,8-dimethylnaphthalene (TDD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA) ); 3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bis(tricyclohexylphosphine)bis Palladium(II) acetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), bis(tricyclohexylphosphine) ) palladium (II) diacetate (Pd785) and dimethylaniline tetrakis (pentafluorophenyl) borate (DANFABA); 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine)diacetate palladium (II) ) (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hept-2,5- Diene (NBD), bis(tricyclohexylphosphine)diacetate palladium (II) (Pd785) and tetrakis (pentafluorophenyl) dimethylaniline borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis( Tricyclohexylphosphine) palladium (II) diacetate (Pd785) and dimethylaniline tetrakis (pentafluorophenyl) borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hept-2,5-diene (NBD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethyl tetrakis(pentafluorophenyl)borate Aniline (DANFABA); and 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a, 9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3), bis(tricyclohexylphosphine) palladium (II) diacetate (Pd785) and tetrakis(penta) Fluorophenyl) dimethylaniline borate (DANFABA). A film-forming kit comprising a composition comprising: a) one or more olefin monomers of the general formula (I):

(I) where m is an integer of 0, 1 or 2;

is a single bond or a double bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, straight-chain or branched (C ₃ -C ₁₆ ) alkyl, perfluoro(C ₁ -C ₁₂ ) alkyl, (C ₃ -C ₁₂ ) cycloalkyl, (C ₆ -C ₁₂ ) bicycloalkyl, (C ₇ -C ₁₄ ) tricycloalkyl, (C ₆ -C ₁₀ )aryl, (C ₆ -C ₁₀ )aryl(C ₁ -C ₆ )alkyl, perfluoro(C ₆ -C ₁₀ )aryl, perfluoro(C ₆ -C ₁₀ ) Aryl (C ₁ -C ₆ ) alkyl, methoxy, ethoxy, straight or branched (C ₃ -C ₁₆ ) alkoxy, epoxy (C ₁ -C ₁₀ ) alkyl, epoxy (C ₁ -C ₁₀ )alkoxy(C ₁ -C ₁₀ )alkyl, epoxy(C ₃ -C ₁₀ )cycloalkyl, perfluoro(C ₁ -C ₁₂ )alkoxy, (C ₃ - C ₁₂ ) cycloalkoxy, (C ₆ -C ₁₂ ) bicycloalkoxy, (C ₇ -C ₁₄ ) tricycloalkoxy, (C ₆ -C ₁₀ ) aryloxy, (C ₆ -C ₁₀ ) ) aryl (C ₁ -C ₆ ) alkoxy group, perfluoro (C ₆ -C ₁₀ ) aryloxy group and perfluoro (C ₆ -C ₁₀ ) aryl (C ₁ -C ₃ ) alkoxy group group; or one of R ₁ and R ₂ and one of R ₃ and R ₄ together with the carbon atoms to which they are bonded form a substituted or unsubstituted (C ₅ -C ₁₄ ) which may have more than one double bond ) ring, (C ₅ -C ₁₄ )bicyclic or (C ₅ -C ₁₄ )tricyclic; b) an organopalladium compound selected from the group comprising: bis(triphenylphosphine)palladium(II) chloride ; Bis(triphenylphosphine)palladium(II) dibromide; Bis(triphenylphosphine)palladium(II) diacetate; Bis(triphenylphosphine)bis(trifluoroacetic acid)palladium(II); Bis(tricyclohexyl) phosphine) palladium(II) dichloride; bis(tricyclohexylphosphine) palladium(II) dibromide; bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785); bis(tricyclohexylphosphine)bis (trifluoroacetic acid)palladium(II); bis(tris-p-tolylphosphine)palladium(II) dichloride; bis(tris-p-tolylphosphine)palladium(II) dibromide; bis(tris-p-tolylphosphine) Palladium(II) diacetate; bis(tri-p-tolylphosphine)bis(trifluoroacetic acid)palladium(II); palladium(II) ethylhexanoate; palladium(II) dichlorobis(benzonitrile); platinum chloride (II); platinum(II) bromide; and bis(triphenylphosphine)platinum dichloride; c) an activator selected from the group consisting of: lithium tetrafluoroborate; lithium trifluoromethanesulfonate; four (Pentafluorophenyl) lithium borate; Tetrakis (pentafluorophenyl) borate lithium ether complex (LiFABA); Tetrakis (pentafluorophenyl) borate sodium ether complex (NaFABA); Tetrakis (pentafluorophenyl) borate trityl ether complex (tritylFABA); tetrakis (pentafluorophenyl) borate trityl ether complex (tropyliumFABA); tetrakis (pentafluorophenyl) borate lithium isopropoxide compound; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexafluorophosphate; Lithium hexafluorophenyl phosphate; Lithium hexafluoroarsenate; Lithium phenylarsenate; Lithium hexa(pentafluorophenyl)arsenate; Lithium hexa(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexa(pentafluorophenyl) antimonate; Lithium hexa(3,5-bis(trifluoromethyl) phenyl) antimonate; Lithium tetrakis(pentafluorophenyl) aluminate; Tris(nonafluorobiphenyl) fluoride Lithium aluminate; lithium (octyloxy)tris(pentafluorophenyl)aluminate; lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; methyltris(pentafluorophenyl)aluminum and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); and d) a solvent selected from the group consisting of water, ortho-xylene, para-xylene, meta-xylene, benzene, fluorobenzene , 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1,2,3 ,4-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, toluene, ethylbenzene, trifluorotoluene, pentafluoroethylbenzene, chlorobenzene, nitrobenzene, 1,4 -Diethane, dimethylacetamide, dimethylformamide, diethylformamide, furan, tetrahydrofuran, diethyl ether, dimethoxyethane, ethyl acetate, propyl acetate, butyl acetate , Amyl acetate, acetone, methyl ethyl ketone, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, ethylcyclopentane, ethylcyclohexane, dibromoethane, Mixtures of dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and any combination of these. The set of claim 11, wherein m is 0;

is a single bond; R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl and norbornyl. The kit of claim 11, wherein the monomer of the aforementioned general formula (I) is selected from the group comprising:

Bicyclo[2.2.1]hept-2-ene (norbornene or NB);

Bicyclo[2.2.1]hept-2,5-diene (norbornadiene or NBD);

5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);

5-Decylbicyclo[2.2.1]hept-2-ene (DecNB);

5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

5-ethylenebicyclo[2.2.1]hept-2-ene (ENB);

5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB);

5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);

5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB);

5-phenylbicyclo[2.2.1]hept-2-ene (PhNB);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

2,2'-bis(bicyclo[2.2.1]heptane-5-ene) (NBANB);

1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD);

2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD);

1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene (TDD);

3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD); and

3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3). The kit according to claim 11, further comprising: a compound selected from the group consisting of the following, a compound of the aforementioned general formula (A1):

(A1) wherein, b is an integer from 2 to 6; Z is a bond or R ₉ R ₁₀ SiOSiR ₁₁ R ₁₂ , wherein each of R ₉ , R ₁₀ , R ₁₁ and R ₁₂ is the same or different, and is independently selected from the group consisting of the group of methyl, ethyl and straight or branched (C3 _{- C6} )alkyl _{; R5} , R6, _R7 and _R8 are the same or different, and are each independently selected from the group consisting of hydrogen, methyl , ethyl and straight-chain or branched (C ₃ -C ₁₆ ) alkyl groups; Compounds of the aforementioned general formula (A2):

(A2) wherein, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different, and are each independently selected from the group consisting of hydrogen, methyl, ethyl and straight or branched (C ₃ -C ₁₆ ) alkyl groups group; and compounds of the aforementioned general formula (A3):

(A3) wherein, L is a bond or a divalent linking group or a spacer group, which is selected from the group consisting of: methylene, ethylidene, straight-chain or branched (C ₃ -C ₁₆ ) alkylene, (C ₃ -C ) ₁₆ ) Cycloalkylene, (C ₅ -C ₈ ) heterocycle, (C ₆ -C ₁₂ ) arylene, (C ₅ -C ₁₂ ) heteroarylene and -(CH ₂ ) _c O(CH ₂ ) _c -, wherein c is an integer from 1 to 6, and each CH ₂ may be substituted by methyl, ethyl, straight or branched (C ₃ -C ₁₆ ) alkyl and (C ₆ -C ₁₂ ) aryl groups, wherein the hydrogen moiety in methylene, ethylidene or (C ₃ -C ₁₆ )alkylene may be selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched perfluoro(C ₃ -C ₁₆ ) group substitution of alkyl groups; R ₁₇ and R ₁₈ are the same or different, and are each independently selected from methyl, ethyl, linear or branched (C ₃ -C ₁₂ ) alkyl , (C ₆ -C ₁₂ ) aryl and (C ₆ -C ₁₂ ) aryl(C ₁ -C ₁₂ ) alkyl groups, wherein the hydrogen moiety in methyl, ethyl or (C ₃ -C ₁₂ ) alkyl groups may be substituted by a group selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched (C ₃ -C ₁₂ ) perfluoroalkyl; Ar ₁ and Ar ₂ are the same or different , and are independently selected from (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₂ ) aryl (C ₆ -C ₁₂ ) aryl (C ₁ -C ₄ ) alkyl and (C ₆ -C ₁₂ ) aryl (C ₁ -C ₄ ) alkoxy groups substituted (C ₆ ) -C ₁₂ ) arylene or (C ₆ -C ₁₂ )heteroarylene. The kit of claim 14, wherein the compound of the aforementioned general formula (A1) is selected from the group comprising:

1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB); and

1,4-Bis(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBC4NB). The kit according to claim 14, wherein the compound of the aforementioned general formula (A2) is

1,4,4a,4b,5,8,8a,8b-Octahydro-1,4:5,8-Dimethylbiphenyl ((NBD)2). The kit of claim 14, wherein the compound of the aforementioned general formula (A3) is selected from the group comprising:

3,3'-((oxobis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazacyclopropene);

4,4''-bis(3-(trifluoromethyl)-3H-diazacyclopropen-3-yl)-1,1':3',1''-bitriphenyl;

3,5-bis(4-(3-(trifluoromethyl)-3H-diazacyclopropen-3-yl)phenyl)pyridine; and

3,3'-((Perfluoropropane-2,2-diyl)bis([1,1'-biphenyl]-4',4-diyl))bis(3-(trifluoromethyl) -3H-diazacyclopropene). A kit as claimed in claim 11, wherein The aforementioned fillers are inorganic fillers. A kit as claimed in claim 11, wherein The aforementioned fillers are organic fillers. The kit of claim 11, selected from the group consisting of: 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 1,4,4a,5,8,8a-hexa Hydrogen-1,4:5,8-dimethylnaphthalene (TDD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA) ; 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB), 1,4,4a,5,8,8a- Hexahydro-1,4:5,8-dimethylnaphthalene (TDD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA) ); 3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bis(tricyclohexylphosphine)bis Palladium(II) acetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methylindene (DCPD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), bis(tricyclohexylphosphine) ) palladium (II) diacetate (Pd785) and dimethylaniline tetrakis (pentafluorophenyl) borate (DANFABA); 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine)diacetate palladium (II) ) (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hept-2,5- Diene (NBD), bis(tricyclohexylphosphine)diacetate palladium (II) (Pd785) and tetrakis (pentafluorophenyl) dimethylaniline borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethylaniline tetrakis(pentafluorophenyl)borate (DANFABA); 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bis( Tricyclohexylphosphine) palladium (II) diacetate (Pd785) and dimethylaniline tetrakis (pentafluorophenyl) borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hept-2,5-diene (NBD), bis(tricyclohexylphosphine) palladium(II) diacetate (Pd785) and dimethyl tetrakis(pentafluorophenyl)borate Aniline (DANFABA); and 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a, 9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3), bis(tricyclohexylphosphine) palladium (II) diacetate (Pd785) and tetrakis(penta) Fluorophenyl) dimethylaniline borate (DANFABA).

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